CN106290437A

CN106290437A - A kind of measure the method for iron content in fireworks and firecrackers ferroso-ferric oxide

Info

Publication number: CN106290437A
Application number: CN201610779725.4A
Authority: CN
Inventors: 吴俊逸
Original assignee: Individual
Current assignee: Individual
Priority date: 2016-08-31
Filing date: 2016-08-31
Publication date: 2017-01-04

Abstract

The invention discloses and a kind of measure the method for iron content in fireworks and firecrackers ferroso-ferric oxide, it comprises the steps: 1) draw calibration curve: 1.1) prepare the many parts of different ferrum working solutions of concentration；1.2) adopt spectrum and draw calibration curve；2) iron content in ferroso-ferric oxide is quickly measured: 2.1) preparation test liquid；2.2) test liquid is analyzed；2.3) content of ferrum in sample is calculated.The present invention is by optimizing sample dissolution condition and each Parameter Conditions of Xray fluorescence spectrometer device, can eliminate or substantially eliminate the matrix effect between each element in sample, directly with iron content in energy dispersion type X-ray fluorescence spectroscopy Accurate Determining fireworks and firecrackers ferroso-ferric oxide.Method is simple to operate, and the detection cycle is short, and labor intensity is low and less demanding to operator, and accuracy is good, and precision is high.

Description

A kind of measure the method for iron content in fireworks and firecrackers ferroso-ferric oxide

Technical field

The present invention relates to the assay method of iron content in ferroso-ferric oxide, especially a kind of fireworks and firecrackers that measures aoxidizes with four The method of iron content in three-iron, belongs to analysis and testing technology field.

Background technology

In prior art, not yet find the standard detecting method of iron content in fireworks and firecrackers ferroso-ferric oxide, the most often Reference method standard " fireworks and firecrackers mensuration the 11st part of chemical raw material key index: iron powder " (SN/T 3056.11-2011) it is based on traditional chemical analysis method.The ultimate principle of this standard method: test portion after suitable pretreatment, First fully dissolve with nitric acid, after sodium hydroxide pellets, precipitation enrichment, filtration, use dissolving with hydrochloric acid filtering residue, take a certain amount of after constant volume Filtrate, in conical flask, regulates pH value of solution 2.0～pH2.5 with hydrochloric acid and ammonia, adds water-bath after a certain amount of hydrochloric acid buffer solution Add sulfosalicylic acid after being heated to 60 DEG C～70 DEG C while hot as indicator solution, be titrated to rice with EDETATE SODIUM standard titration solution The colour-fast terminal that is of yellow 30s, calculates the amount tapped a blast furnace.

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 after dissolving with nitric acid, 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) side Method requires height to experimenter, and in operating procedure, many places relate to washing, shift, dissolve, filter, reprecipitation, are enriched with, dissolve, adjust Joint pH value and titration etc. are readily incorporated probabilistic operating procedure, each test operation personnel must significant care and careful, Otherwise it is 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).Using energy dispersion type Xray fluorescence spectrometer to carry out assay with simple to operate, the detection cycle is short, and accuracy Good, precision height is widely used in the quick analysis of inorganic elements.

The ferroso-ferric oxide material quality used due to different types of fireworks and firecrackers goods is widely different, its impurity Chemical composition is also not quite similar and extremely complex, and some factories the most directly use four that the lowest and impurity component of taste is complicated The raw material that Fe 3 O makes as firework medicament uses.Matrix effect (the bag of complexity is there is between ferroso-ferric oxide element Include absorption-enhancement effect and physical-chemical effect between element), it is impossible to utilize energy dispersion type X-ray fluorescence spectroscopy (EDXRF) powder pressing method and fusion method is directly used to measure the solid powder sample that matrix background is complicated and changeable.Up to now Also there are no the open source literature report of iron content in energy dispersion type X-ray fluorescence spectroscopy detection fireworks and firecrackers ferroso-ferric oxide Road.

Summary of the invention

The present invention provides a kind of and measures the method for iron content in fireworks and firecrackers ferroso-ferric oxide, by optimizing sample dissolution Each Parameter Conditions of condition and Xray fluorescence spectrometer device eliminates or substantially eliminates the matrix effect in sample between each element, directly Connecing and go out iron content in fireworks and firecrackers ferroso-ferric oxide with energy dispersion type X-ray fluorescence spectroscopy Accurate Determining, method operates Simply, the detection cycle is short, and labor intensity is low and less demanding to operator, and accuracy is good, and precision is high.

The technical solution used in the present invention is:

A kind of measure the method for iron content in fireworks and firecrackers ferroso-ferric oxide, comprise the steps:

1) calibration curve is drawn:

1.1) prepare many parts of ferrum working solutions: weigh the reference material of ferrum, add nitric acid and dissolve, be transferred to volumetric flask also It is settled to certain volume with water, obtains certain density ferrous solution, then pipette the ferrous solution of many parts of different volumes to different Volumetric flask also uses water constant volume, obtains the ferrum working solution of different quality concentration；Controlling the mass concentration of Fe in ferrum working solution is 0.08g/L～0.66g/L；

1.2) with energy dispersion type Xray fluorescence spectrometer as detecting instrument, the sample supposed for calibration curve with 2.0g Amount, the intensity correction mathmetic correction of employing X fluorescence spectrum quantitative analysis sets up analysis method, aperture is 8.8mm～14mm X-ray light pipe collimator and the energy filter of X-ray less than 7.111KeV can be filtered, arrange voltage be 16KV～ 24KV, analysis time is 30s～80s, and energy range is 0～40KeV, and during counting rate is, gaseous environment is air, and electric current is certainly Dynamic, matrix effect is not for consider；

By step 1.1) mass concentration of Fe is converted into the mass percent concentration of Fe, so in many parts of ferrum working solutions preparing After sample introduction one by one, record the fluorescence intensity of the Fe of each sample introduction, the mass percent concentration of Fe in each ferrum working solution is for horizontal seat Mark, with the fluorescence intensity corresponding with the mass percent concentration of above-mentioned Fe as vertical coordinate, makes calibration curve；Wherein, by under State formula and the mass concentration of Fe in ferrum working solution be converted into the mass percent concentration of Fe:

F e % = \frac{c \times 0.5}{2} \times 100 %

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；

2) iron content in ferroso-ferric oxide is quickly measured:

2.1) preparation test liquid: with ferroso-ferric oxide raw material as sample, during preparation test liquid, weighs sample and is accurate to 0.1mg, is placed in beaker, adds a certain amount of nitric acid, places and heats micro-boiling 30min on electric furnace, while hot with filter paper filtering, filtrate is received Collection, to volumetric flask, adds water after the solution in volumetric flask is cooled to room temperature and is settled to scale；Wherein, according to 60mL/g～80mL/g The amount of sample adds nitric acid；On the basis of 0.3g～0.4g sample constant volume to 500mL, calculate sample during constant volume answer the concrete of constant volume Volume；

2.2) detection test liquid: by step 1.2) testing conditions, test liquid is loaded specimen cup, it is ensured that sample liquid thickness >= 15mm, the fluorescence intensity of display on grapher, read corresponding with this fluorescence intensity according to the above-mentioned calibration curve determined Fe mass percent concentration value；

2.3) content of ferrum in calculating sample:

The mass percent concentration of fe in calculating sample as follows:

ω = ω_{0} \times \frac{2}{m} \times \frac{V}{500}

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 0.4g；V is the volume of actual constant volume after representing sample dissolution, and unit is mL； 500 represent the volume supposing sample size constant volume, and unit is mL.

Preferably, step 1.1) in, the ferrous solution pipetting 5-15 part different volumes prepares ferrum working solution.

Preferably, step 1.1) in, the reference material of ferrum is high-purity iron powder.

Preferably, step 1.1) in, add nitric acid, HNO in nitric acid according to the amount of 60mL/g～80mL/g sample₃Quality Percent concentration is 40%～60%.

Preferably, step 1.2) in, the X-ray light pipe collimator using aperture to be 8.8mmm, use thin Pd filter, arrange Voltage is 20KV, and analysis time is 50s, and energy range is 0～20KeV.

Preferably, HNO in nitric acid₃Mass percent concentration be 40%～60%.

Preferably, step 2.1) in, the quality weighing sample is 0.3g～0.4g.

It is further preferred that step 2.2) in, sample liquid thickness is 15mm～30mm.

In order to ensure the accuracy of test result, in the matrix effect considering energy dispersion type Xray fluorescence spectrometer On the basis of, and carried out sample size and the actual sample amount that substantial amounts of test finally determines that selected 2.0g is calibration curve supposition Take 0.3g～0.4g.

The ultimate principle of the inventive method: first, for the fireworks and firecrackers feature of ferroso-ferric oxide chemical composition, sets up Special mathematical model, global optimization can directly affect each factor of measurement result, including: dissolve the solvent kind of test portion Class, chemical composition and volume number, test portion dissolution conditions, test solution constant volume, for setting up the matrix effect mathematics of analysis method Correction method type, for make calibration curve test portion suppose sample size, series standard solution matrix composition, concentration range and The interval of standard solution point value and quantity, the actual sample weighting amount of test portion and the matrix effect phase of energy dispersion type X fluorescence spectrum instrument The work in every ginsengs such as interaction form, voltage, electric current, the selection of filter, analysis time, counting rate, gaseous environment, energy range The thickness etc. of test solution in number and specimen cup.Select nitric acid to dissolve test portion as solvent, be on the one hand can be the most molten based on nitric acid The consideration containing Fe elemental composition such as the ferroso-ferric oxide in solution test portion, is on the other hand also based on examining of nitric acid solvent compositing characteristic Consider, nitric acid contains only tri-kinds of elements of H, N and O, and the introducing of these three element will not produce the interference of matrix effect to test； Again, global optimization test portion dissolution conditions, test solution constant volume, for setting up the matrix effect mathmetic correction class of analysis method Type, the test portion of making calibration curve suppose matrix composition, concentration range and the standard solution point value of sample size, series standard solution Interval and quantity, the actual sample weighting amount of test portion and the matrix effect interaction type of energy dispersion type X fluorescence spectrum instrument, electricity In the work in every parameters such as pressure, electric current, the selection of filter, analysis time, counting rate, gaseous environment, energy range and specimen cup In the work in every parameters such as the thickness of test solution and specimen cup, the thickness etc. of test solution directly affects each factor of measurement result, passes through The supposition sample size of global design test portion, the sample size of actual sample, every test parameter of Xray fluorescence spectrometer, it is used for The crucial Testing factors such as the matrix composition of the series standard solution of making calibration trace and concentration span of control thereof, set up special pin To the calibration trace of Fe element determination in fireworks and firecrackers ferroso-ferric oxide, in this test condition, due in sample test solution The elements such as other metallic element concentration are relatively low, H and O belong to the light element that Xray fluorescence spectrometer is insensitive, and Fe element Matrix effect is negligible in calibration trace standard point interval concentration range, thus realizes targeting and control in test solution between each element Matrix effect；Finally, can determine whether to adjust sample according to the diversity of all kinds fireworks and firecrackers ferroso-ferric oxide sample This amount, carries out the quantitative analysis of Fe element based on this calibration trace.The method is simple to operate, the detection cycle is short, and testing result Accuracy is good, and precision is high.

The present invention utilizes solwution method eliminate or substantially eliminate matrix effect, thus can directly use energy dispersion type X-ray Fluorescent spectrometry Accurate Determining goes out the iron content in fireworks and firecrackers ferroso-ferric oxide；

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, and the analysis obtained is tied Fruit more can represent whole analysis sample；

(2) composition of Macrodilution based on solvent, sample and standard specimen is close to the composition of solvent, and solvent is mainly by light unit Element composition, absorption-enhancement effect becomes the least, and matrix effect substantially can not consider；It is additionally, since X-ray to penetrate deeply Degree is relatively deep, and fluorescent radiation absorbs less, so higher absolute sensitivity can be obtained；

(3) if solution made by the sample that standard specimen is difficult to obtain, calibration curve can use standard reagent to synthesize, and estimates the back of the body The blank sample of the factors such as scape is readily made；

(4) constant volume is to certain volume after water-soluble for sample, and in test liquid, H in addition to Fe element, O, N element are to Fe element The matrix effect produced is the least, is negligible.

Use and have the beneficial effects that produced by technique scheme:

1, solwution method is utilized to eliminate or substantially eliminate matrix effect, directly accurate with energy dispersion type X-ray fluorescence spectroscopy Really determining iron content in fireworks and firecrackers ferroso-ferric oxide, method is simple to operate, and labor intensity is low and to operator's requirement The highest.

2, the present invention is after establishing calibration curve, whole mensuration process only include sample weighing, dissolve, shift constant volume, 4 easy steps such as examination with computer, total time-consuming less than 2h, labor intensity is low and less demanding to operator.

3, using the method for the present invention to detect, accuracy is good, and precision is high.

Accompanying drawing explanation

The present invention is further detailed explanation with detailed description of the invention below in conjunction with the accompanying drawings.

Fig. 1 is the calibration curve of the mass percent concentration-fluorescence intensity of the Fe that inventive embodiments 1 obtains；

The mass percent concentration of Fe during wherein abscissa is each ferrum working solution, unit is %；Vertical coordinate is and above-mentioned Fe Fluorescence intensity corresponding to mass percent concentration, 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～0.66g/ 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 60mL/g～80mL/g The amount of sample adds nitric acid；, beaker is placed on electric furnace heating 25min～30min, is transferred to after solution is cooled to room temperature 500mL volumetric flask, adds water and is settled to scale；Wherein, HNO in nitric acid₃Mass percent concentration be 40%～60%.

Prepare 8 parts of ferrum working solutions: pipette respectively the ferrous 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 obtain numbered work 1, work 2, The ferrum working solution of 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；

F e % = \frac{c \times 0.5}{2} \times 100 %

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.

Fe concentration and the fluorescence intensity of correspondence in table 1 ferrum working solution

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., each method of described energy dispersion type Xray fluorescence spectrometer Parameter is as shown in table 2；

Table 2 energy dispersion type Xray fluorescence spectrometer parameter

Filter

Voltage

Electric current

Analysis time

Counting rate

Gaseous environment

Matrix effect

Energy range

Thin Pd

20Kv

Automatically

50s

In

Air

Do not consider

0～20Kev

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 controlled trial that fireworks and firecrackers ferroso-ferric oxide reference material is measured by the method for the invention

Testing with reference material listed in table 3, wherein the ferrum nominal content of reference material is as shown in table 3；Use When the method for the invention measures, reference material carries out iron content mensuration after preparing test liquid as follows again.

1) preparation test liquid:

Prepare test liquid with the reference material of numbering 1 for sample, weigh 3 parts of 0.3g～0.4g sample, be accurate to when weighing 0.1mg, the 1st part of sample is placed in 300mL beaker, adds nitric acid according to the amount of 60mL/g～80mL/g sample, places electric furnace electricity Heat micro-boiling 30min on stove, while hot with filter paper filtering, by filtrate collection to 500mL volumetric flask, treat the solution cooling in volumetric flask Add water to room temperature and be settled to scale and obtain the 1st part of test liquid；Repeat said method, obtain 3 parts of samples of No. 1 reference material Liquid；

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:

ω = ω_{0} \times \frac{2}{m} \times \frac{V}{500}

Wherein, ω represents the mass percent concentration of ferrum in sample, and unit is %；ω₀Represent and read according to calibration curve Fe mass percent concentration value, unit is %；2 represent the sample size that calibration curve supposes, unit is g；M represents that sample is actual The quality weighed, unit is g, typically weighs 0.3g～0.4g；V represents the volume of constant volume after sample dissolution, and unit is mL；500 Representing the volume supposing sample size constant volume, 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 2-8, calculates them respectively Iron content and the response rate, the results are shown in Table 3.

Table 3 controlled trial data

As shown in Table 3, the method for the invention is to the ferrum element in the fireworks and firecrackers ferroso-ferric oxide of different iron contents Measure and there is good accuracy.

Embodiment 3

Use the method for the invention precision test to the testing result of ferroso-ferric oxide reference material

In the present embodiment, the ferroso-ferric oxide reference material with three different iron contents is tested for sample, numbered 4, 5 and 6.

1) preparation test liquid:

Prepare test liquid with the reference material of numbering 4 for sample, weigh 4 parts of 0.3g～0.4g sample, be accurate to when weighing 0.1mg, the 1st part of sample is placed in 300mL beaker, adds nitric acid according to the amount of 60mL/g～80mL/g sample；Place on electric furnace Heat micro-boiling 30min, 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 the sample liquid thickness of each sample introduction is 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 5.

ω = ω_{0} \times \frac{2}{m} \times \frac{V}{500}

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 precision test data

As shown in Table 4, ferrum element in the ferroso-ferric oxide of different main content is measured and has well by the method for the invention Precision, maximum allowable difference is 0.5%.

Embodiment 4

The mensuration of iron content in actual fireworks and firecrackers ferroso-ferric oxide

1, for the fireworks and firecrackers ferroso-ferric oxide sample of detection:

1#: sample from Hepu County Guangxi fireworks station-service in produce spraying decoration class fireworks ferroso-ferric oxide raw material.

2#: sample from Lingshan County, Guangxi fireworks station-service in produce 5 cun of display shell class samples the former material of ferroso-ferric oxide Material.

2, use the method for the invention that above-mentioned ferroso-ferric oxide 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:

Weigh 1# ferroso-ferric oxide sample 0.3g～3 parts of 0.4g sample respectively, when weighing, be accurate to 0.1mg, the 1st part of sample Be placed in 300mL beaker, and press respectively 60mL/g, 70mL/g, 80mL/g sample amount add nitric acid (in this step, 3 parts of samples It is respectively adopted the nitric acid that weight/mass percentage composition is 60%, 50% and 40%), place and on electric furnace, heat micro-boiling 30min, while hot with filter Paper filters, and by filtrate collection to 500mL volumetric flask, adding water after the solution in volumetric flask is cooled to room temperature is settled to scale and obtains 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 ferroso-ferric oxide:

By embodiment 1 step 2b) testing conditions, by 3 parts of test liquid sample introductions one by one of 1# ferroso-ferric oxide sample, load The sample path length of specimen cup is 15mm, and on grapher, the fluorescence intensity of display, determines according to embodiment 1 with this fluorescence intensity Calibration curve reads corresponding Fe mass percent concentration value；

Calculating the mass percent concentration of ferrum in 1# ferroso-ferric oxide sample the most as follows, result is as shown in table 5.

ω = ω_{0} \times \frac{2}{m} \times \frac{V}{500}

Wherein, ω represents the mass percent concentration of ferrum in sample, and unit is %；ω₀Represent and read according to calibration curve Fe mass percent concentration value, unit is %；2 represent the sample size that calibration curve supposes, unit is g；M represents that sample is actual The quality weighed, unit is g；V represents the volume of constant volume after sample dissolution, and unit is mL；500 represent supposition sample size constant volume Volume, unit is mL.

By the compound method of the test liquid of above-mentioned 1# ferroso-ferric oxide sample, prepare the examination of 2# ferroso-ferric oxide sample respectively Sample liquid, and calculate its iron content, the results are shown in Table 5.

While measuring above-mentioned ferroso-ferric oxide sample by this method, referring also to using existing traditional chemical analysis side Method (" fireworks and firecrackers mensuration the 11st part of chemical raw material key index: iron powder " (SN/T 3056.11-2011)) Being detected above-mentioned sample, result is as described in Table 5.

The determination data table of iron content in table 5 actual fireworks and firecrackers ferroso-ferric oxide sample

Claims

1. one kind measures the method for iron content in fireworks and firecrackers ferroso-ferric oxide, it is characterised in that it comprises the steps:

1) calibration curve is drawn:

1.1) prepare many parts of ferrum working solutions: weigh the reference material of ferrum, add nitric acid and dissolve, be transferred to volumetric flask and use water It is settled to certain volume, obtains ferrous solution, pipette ferrous solution extremely multiple volumetric flasks the constant volume of many parts of different volumes the most respectively, Obtain the ferrum working solution of different quality concentration；Making the mass concentration of Fe in ferrum working solution is 0.08g/L～0.66g/L；

1.2) with energy dispersion type Xray fluorescence spectrometer as detecting instrument, the sample size supposed for calibration curve with 2.0g, adopt With the X-ray light pipe collimator that aperture is 8.8mm～14mm, it is possible to filter the filter of the energy X-ray less than 7.111KeV, if Putting voltage is 16KV～24KV, and analysis time is 30s～80s, and energy range is 0～40KeV, during counting rate is, and gaseous environment For air, electric current is that matrix effect is not for consider, and uses the intensity correction method of X fluorescence spectrum quantitative analysis to set up automatically Analysis method；

By step 1.1) mass concentration of Fe is converted into the mass percent concentration of Fe in many parts of ferrum working solutions preparing, then by One sample introduction, records the fluorescence intensity of each sample introduction, and the mass percent concentration of Fe in each ferrum working solution is as abscissa, with upper The fluorescence intensity stating the mass percent concentration of Fe corresponding is vertical coordinate, makes calibration curve；Wherein, by following formula by ferrum In working solution, the mass concentration of Fe is converted into the mass percent concentration of Fe:

F e % = \frac{c \times 0.5}{2} \times 100 %

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；

2) iron content in ferroso-ferric oxide is quickly measured:

2.1) preparation test liquid: with fireworks and firecrackers ferroso-ferric oxide raw material as sample, weigh a certain amount of sample, be accurate to 0.1mg, is placed in beaker, adds a certain amount of nitric acid, places and heats micro-boiling 25min～30min on electric furnace, uses filter paper mistake while hot Filter, by filtrate collection to volumetric flask, adds water after the solution in volumetric flask is cooled to room temperature and is settled to scale；Wherein, according to The amount of 60mL/g～80mL/g sample adds nitric acid；On the basis of 0.3g～0.4g sample constant volume to 500mL, examination is calculated during constant volume The concrete volume of constant volume answered by sample；

2.2) detection test liquid: by step 1.2) testing conditions, test liquid is loaded specimen cup, it is ensured that sample liquid thickness >= 15mm, the fluorescence intensity of the Fe of display on grapher, read and it according to the above-mentioned calibration curve determined with this fluorescence intensity Corresponding Fe mass percent concentration value；

2.3) content of ferrum in calculating sample:

The mass percent concentration of fe in calculating sample as follows:

ω = ω_{0} \times \frac{2}{m} \times \frac{V}{500}

Wherein, ω represents the mass percent concentration of fe in sample, and unit is %；ω₀Represent according to calibration curve reading Fe mass percent concentration value, unit is %；2 represent the sample size that calibration curve supposes, unit is g；M represents that sample is actual and claims The quality of amount, unit is g；V represents the volume of constant volume after sample dissolution, and unit is mL；500 represent the body supposing sample size constant volume Long-pending, unit is mL.

The most according to claim 1 a kind of measuring the method for iron content in fireworks and firecrackers ferroso-ferric oxide, its feature exists In described step 1.1) in, the ferrous solution pipetting 5～15 parts of different volumes prepares ferrum working solution.

The most according to claim 1 a kind of measuring the method for iron content in fireworks and firecrackers ferroso-ferric oxide, its feature exists In described step 1.1) in, described nitric acid adds according to the amount of 60mL/g～80mL/g sample, HNO in nitric acid₃Percent mass Specific concentration is 40%～60%.

The most according to claim 1 a kind of measuring the method for iron content in fireworks and firecrackers ferroso-ferric oxide, its feature exists Reference material in described ferrum is high-purity iron powder.

The most according to claim 1 a kind of measuring the method for iron content in fireworks and firecrackers ferroso-ferric oxide, its feature exists In described step 1.2) in, the X-ray light pipe collimator using aperture to be 8.8mmm, use thin Pd filter, arranging voltage is 20KV, analysis time is 50s, and energy range is 0～20KeV.

The most according to claim 1 a kind of measuring the method for iron content in fireworks and firecrackers ferroso-ferric oxide, its feature exists HNO in described nitric acid₃Mass percent concentration be 40%～60%.

The most according to claim 1 a kind of measuring the method for iron content in fireworks and firecrackers ferroso-ferric oxide, its feature exists In described step 2.1) in, the quality weighing sample is 0.3g～0.4g.

A kind of fireworks and firecrackers that measures the most according to claim 1 weighs the method for iron content in potassium ferrite, it is characterised in that Described step 2.2) in, sample liquid thickness is 15mm～30mm.