CN106370686A - Method for determining copper content in basic copper carbonate for fireworks and firecrackers - Google Patents
Method for determining copper content in basic copper carbonate for fireworks and firecrackers Download PDFInfo
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- CN106370686A CN106370686A CN201610776406.8A CN201610776406A CN106370686A CN 106370686 A CN106370686 A CN 106370686A CN 201610776406 A CN201610776406 A CN 201610776406A CN 106370686 A CN106370686 A CN 106370686A
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
The invention discloses a method for determining the copper content in basic copper carbonate for fireworks and firecrackers. The method uses an energy-dispersion X-ray fluorescence spectrophotometer as a detecting instrument and comprises the following steps: 1) drawing of calibration curve: preparing multiple copper working solutions with different concentrations, and drawing a calibration curve by using the mass percents of Cu in the copper working solutions as horizontal ordinates and the fluorescence intensities corresponding to the mass percents of Cu as vertical coordinates; and 2) determination of copper content in basic copper carbonate: preparing a sample solution, recording the fluorescence intensity of Cu displayed on the instrument, reading the mass percent of Cu corresponding to the fluorescence intensity according to the calibration curve in the step 1), and calculating the mass percent of the simple substance copper in the sample according to the formula. The method is simple to operate, and has the advantages of short detection period, favorable accuracy of detection results and high precision.
Description
Technical field
The invention belongs to analysis and testing technology field is and in particular to a kind of measure copper in fireworks and firecrackers basic copper carbonate and contain
The method of amount.
Technical background
In prior art, in fireworks and firecrackers basic copper carbonate, the detection method of copper content is based on traditional chemical analysis side
Method, the method standard commonly used at present is " mensure the 4th part of fireworks and firecrackers chemical raw material key index: basic copper carbonate "
(sn/t 3056.4-2011).The ultimate principle of this standard method: after test portion hydrochloric acid fully dissolves, by edta complexometry
Method with pan as indicator solution, uses basic copper carbonate standard under conditions of ph10.0.Volumetric soiutions titration test solution is by yellow to blueness
It is terminal.Record cu in test solution2+And fe3+Fe is deducted after the summation of content3+Amount can obtain the amount of copper.
This standard methods described 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.In addition, being easy to not draw because of testing crew skilled operation degree in concrete process of the test
Enter to cause the uncertainty of measuring result error.(2) operating procedure is relatively complicated, and sample is filtered with after dilute sulfuric acid dissolving, constant volume
Copper ion and the total amount of iron ion to be determined with different methods respectively afterwards and iron ion is individually measured, total amount deducts iron ion
Amount just can draw the amount of copper ion.(3) method has high demands to experimenter, in operating procedure be related to liquid relief, adjust ph value,
Titration etc. is readily incorporated probabilistic operating procedure, and each test operation personnel must significant care and careful, otherwise very
It is readily incorporated artificial uncertainty.
The method that energy dispersion type x-ray fluorescence spectrophotometer is developed at present is used for the nondestructive analysis of sample.For solid
Body sample sxemiquantitative and quantitative elemental detection, most samples adopt nondestructive determination, powder pressing method and fusion method direct
Measure (such as: " the mensure x-ray fluorescent spectrometry of bullion content " (gb/t 18043-2008) uses nondestructive determination,
" aluminium oxide chemical analysis method and method for measuring physical properties the 30th part x-ray fluorescence spectrum method for measuring constituent content " (gb/
T6609.30 2009) use fusion method, " edxrf method directly measures w-fe-ni-co alloy batch component " (" nuclear power
Son is learned and Detection Techniques " 05 phase in 2007) use pressed disc method, " regulated substance lead in electronic and electrical equipment, hydrargyrum, chromium, cadmium and
The rapid screening x-ray fluorescent spectrometry of bromine " (gb/z 21277-2007) use pressed disc method or fusion method).
Because the basic copper carbonate material quality that different types of fireworks and firecrackers product uses is widely different, its chemical group
Become also to be not quite similar and extremely complex, some factories are even directly using the very low and complicated basic copper carbonate of impurity component of taste
Use as raw material.The matrix effect that there is complexity in basic copper carbonate raw material between element (includes absorbing between element-increasing
Potent should be with physical-chemical effect) it is impossible to using energy dispersion type x-ray fluorescent spectrometry (edxrf) directly using powder pressure
Piece method and fusion method measure matrix background solid powder sample complicated and changeable.Up to now also have no based on collective effect targeting
The energy dispersion type x-ray fluorescent spectrometry of control technology (solwution method) detects copper content in fireworks and firecrackers basic copper carbonate
Open source literature is reported.
Content of the invention
It is an object of the invention to provide a kind of method measuring copper content in fireworks and firecrackers basic copper carbonate, operation letter
Single, detection cycle is short, and testing result accuracy is good, and precision is high.
For achieving the above object, the present invention measure fireworks and firecrackers basic copper carbonate in copper content method, including with
Lower step:
1) draw calibration curve:
1.1) many parts of copper working solutions are prepared, the wherein mass concentration of cu controls in 0.10g/l～0.83g/l scope；
1.2) with energy dispersion type x-ray fluorescence spectrophotometer as detecting instrument, the sample that supposed for calibration curve with 2.0g
Amount, the intensity correction method using x fluorescence spectrum quantitative analysis sets up analysis method；By step 1.1) many parts of coppersmiths preparing make
In liquid, the mass concentration of cu is converted into the mass percent concentration of cu, then sample introduction one by one, records the fluorescence of the cu of each sample introduction
Intensity, the mass percent concentration of the cu with each copper working solution as abscissa, with corresponding with the mass percent concentration of above-mentioned cu
Fluorescence intensity be vertical coordinate, make calibration curve；Wherein, by following formula, the mass concentration of cu in copper working solution is converted
The mass percent concentration of one-tenth cu:
Wherein, cu% represents the mass percent concentration of cu in copper working solution, and unit is %；C represents cu in copper working solution
Mass concentration, unit be 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) the quick copper content measuring in basic copper carbonate:
2.1) prepare test liquid: with basic copper carbonate as sample, when preparing test liquid, weigh a certain amount of sample, weigh
When be accurate to 0.1mg, be placed in beaker, add a certain amount of nitric acid, place electric furnace on heat micro-boiling 25min～30min, use while hot
Filter paper filtering, filtrate collection to volumetric flask adds water after the solution in volumetric flask is cooled to room temperature and is settled to certain volume；
2.2) press step 1.2) testing conditions, test liquid is loaded specimen cup it is ensured that sample liquid thickness >=15mm, monitor
The fluorescence intensity of display on device, reads corresponding cu percent mass with this fluorescence intensity according to the calibration curve of above-mentioned determination
Specific concentration value；
2.3) calculate sample in copper content:
As follows calculate sample in copper mass percent concentration:
Wherein, ω represents the mass percent concentration of copper in sample, and unit is %；ω0Represent and read according to calibration curve
Cu mass percent concentration value, unit be %；2 represent the sample size that calibration curve supposes, unit is g；M represents that sample is actual
The quality weighing, unit is g；The volume of v actual constant volume after representing sample dissolution it is ensured that in solution after constant volume the concentration of cu exist
Calibration curve scope, unit is ml；500 represent the volume supposing sample size constant volume, and unit is ml.
Further, described step 1.1) in, the method preparing copper working solution is: weighs a certain amount of high-purity cupric oxide powder
Or other copper reference materials, add appropriate nitric acid to be dissolved, obtain copper solution after being settled to certain volume, then move respectively
Take the copper solution of different volumes, be settled to the copper working solution obtaining variable concentrations after certain volume with water respectively；Wherein, coppersmith is made
The mass concentration of the cu of liquid controls in 0.10g/l～0.83g/l scope.This concentration range is considering energy color through applicant
On the basis of the matrix effect of scattered type x-ray fluorescence spectrophotometer, carry out what substantial amounts of test determined, changing this numerical value will shadow
Ring the accuracy of test result.
Preferably, described step 1.1) in, the volume mass of nitric acid and high-purity cupric oxide powder than for 40ml/g～60ml/g,
The mass percent concentration of nitric acid is 40%～60%.
Preferably, described step 1.1) in, the mass percent concentration of nitric acid is 51%.
Further, described step 1.2) in, testing conditions are: accurate using the x-ray light pipe for 8.8mm～14mm for the aperture
Straight device, can filter the filter that energy is less than the x-ray of 8.980kev, and setting voltage is 16kv～24kv, and analysis time is 30s
～80s, energy range is 0～40kev, and during counting rate is, gaseous environment is air, and electric current is automatic, and matrix effect is not examine
Consider.
Preferably, described step 1.2) in, testing conditions are: using the x-ray light pipe collimator for 8.8mm for the aperture, if
Putting filter is middle pd, and setting voltage is 20kv, and analysis time is 50s, and energy range is 0～20kev.
Preferably, described step 2.1) in, the amount of weighing of sample is 0.29g～0.31g.This range of weighing is through applicant
On the basis of the matrix effect considering energy dispersion type x-ray fluorescence spectrophotometer, carry out what substantial amounts of test determined, changed
Moving this numerical value will affect the accuracy of test result.
Preferably, described step 2.1) in, nitric acid is added by the amount of 60ml/g～80ml/g sample, the quality of nitric acid
Percent concentration is 40%～60%.
Preferably, described step 2.2) in, sample liquid thickness is 15mm～30mm.
The substantive distinguishing features of the present invention and progress are:
The ultimate principle of the inventive method: for the fireworks and firecrackers feature of basic copper carbonate chemical composition, set up special
Mathematical model, global optimization can directly affect each factor of measurement result, including the solvent species of: dissolving test portion,
Chemical composition and volume number, test portion dissolution conditions, test solution constant volume, the matrix effect Mathematical Correction for setting up analysis method
Method type, test portion supposition sample size, the matrix composition of series standard solution, concentration range and standard for making calibration curve
The interval of solution point value and the matrix effect phase interaction of the actual sample weighting amount of quantity, test portion and energy dispersion type x fluorescence spectrum instrument
With work in every parameters such as form, voltage, electric current, the selection of filter, analysis time, counting rate, gaseous environment, energy ranges and
Thickness of test solution etc. in specimen cup.First, select nitric acid to dissolve test portion as solvent, be on the one hand fully to be dissolved based on nitric acid
The consideration of basic copper carbonate component in test portion, is on the other hand also based on the consideration of nitric acid compositing characteristic, contains only h, o in nitric acid
With tri- kinds of elements of n, and the introducing of these three elements will not to test produce matrix effect interference；Secondly, global optimization test portion
Dissolution conditions, test solution constant volume, for setting up the matrix effect mathmetic correction type of analysis method, making calibration curve
Test portion supposes sample size, the interval of matrix composition, concentration range and standard solution point value of series standard solution and quantity, test portion
The matrix effect interaction type of actual sample weighting amount and energy dispersion type x fluorescence spectrum instrument, voltage, electric current, the choosing of filter
Select, analysis time, counting rate, gaseous environment, the items such as thickness of test solution in the work in every parameter such as energy range and specimen cup
In running parameter and specimen cup, thickness of test solution etc. directly affects each factor of measurement result, sets up and is specifically designed for fireworks and firecrackers
With the calibration trace of cu element determination in basic copper carbonate, in this test condition, due to the other impurities unit in sample test solution
Plain concentration is relatively low, and h, o and n element belongs to the insensitive light element of x-ray fluorescence spectrophotometer, when the matrix effect of cu element exists
Calibration trace standard point interval concentration range is negligible, thus realizing targeting to control the matrix effect between each element in test solution
Should；Finally, can determine whether to adjust sample size according to the diversity of all kinds fireworks and firecrackers basic carbonate copper sample, be based on
This calibration trace carries out the quantitative analyses of cu element.The method is simple to operate, detection cycle is short, and testing result accuracy is good,
Precision is high.
Compared with prior art, the having the beneficial effect that of the method for the invention
1st, eliminated using solwution method or substantially eliminate matrix effect, thus can directly use energy dispersion type x-ray fluorescence
Spectrographic method Accurate Determining goes out the copper content in fireworks and firecrackers basic copper carbonate；Eliminate or substantially eliminate matrix effect using solwution method
Answer and its advantage is in particular in: (1) liquor sample eliminates the intrinsic inhomogeneities of solid sample and physical-chemical effect
Should, the analysis result obtaining more can represent whole analysis sample；(2) Macrodilution based on solvent, the composition of sample and standard specimen
Close to the composition of solvent, and solvent is mainly made up of light element, and absorption-enhancement effect becomes very little, and matrix effect is substantially
Can not consider；It is additionally, since x-ray penetration depth deeper, fluorescent radiation absorbs less, so higher absolute spirit can be obtained
Sensitivity；(3) if solution made by the sample that standard specimen is difficult to obtain, calibration curve can estimate background using standard reagent synthesis
It is readily made etc. the blank sample of factor；(4) sample through nitric acid dissolving constant volume to certain volume, in test liquid except cu element with
The matrix effect very little that outer h, o and n element and some impurity elements other produce to cu element, is negligible.
2nd, the method for the invention is simple to operate, and detection cycle is short, and after establishing calibration curve, whole measurement process is only
Including 4 easy steps such as sample weighing, dissolving, transfer constant volume, examination with computers, total time-consuming is less than 2h, and labor intensity is relatively low
And it is less demanding to operator.
3rd, detected using the method for the invention, accuracy is good, precision is high.
Brief description
Fig. 1 is the calibration curve of the mass percent concentration-fluorescence intensity of the cu obtaining for inventive embodiments 1, wherein horizontal
Coordinate is the mass percent concentration of cu in each copper working solution, and unit is %；Vertical coordinate is dense with the mass percent of above-mentioned cu
Spend corresponding fluorescence intensity, unit is cps/ma.
Specific embodiment
Further illustrate technical scheme below by specific embodiment, but the invention is not limited in that these are real
Apply example.
Embodiment 1
Making calibration curve:
1) prepare many parts of copper working solutions (require the mass concentration of cu in the copper working solution of gained control 0.10g/l～
0.83g/l scope):
Specific compound method is with reference to as follows:
Accurately weigh 1.31g high-purity cupric oxide powder (being accurate to 0.1mg), be placed in 300ml beaker, according to nitric acid with high-purity
The volume mass of the amount of copper oxide adds nitric acid than for 40ml/g～60ml/g, by beaker be placed on electric furnace heating 25min～
35min, is cooled to after room temperature after solution and is transferred to 500ml volumetric flask, add water and be settled to scale；Wherein, the quality hundred in nitric acid
Specific concentration is divided to be 40%～60%.
Prepare 8 parts of copper working solutions: pipette respectively the copper 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, mix, number respectively be work 1, work 2, work 3,
Work 4, work 5, work 6, work 7 and work 8, in them, cu concentration is shown in Table 1.
2) draw calibration curve:
2a) with energy dispersion type x-ray fluorescence spectrophotometer (power ＆ light company of the U.S. (thermo electron
Corporation) produce, model quant ' x edxry analyzer) it is detecting instrument, supposed with 2.0g for calibration curve
Sample size, by step 1) mass concentration of cu is become the percent mass of cu by following formula scales in many parts of copper working solutions preparing
Specific concentration, the results are shown in Table 1；
Wherein, cu% represents the mass percent concentration of cu in copper working solution, and unit is %；C represents copper working solution
The mass concentration of middle cu, 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) in energy dispersion type x-ray fluorescence spectrophotometer, 8.8mm x-ray light pipe standard is installed and puts device it is ensured that detector
Temperature prepares to set up assay method after being down to 190k；Intensity correction method using x fluorescence spectrum quantitative analysis sets up analysis side
Pd filter in method, and employing, setting voltage is 20kv, and analysis time is 50s, and energy range is 0～20kev, during counting rate is,
Gaseous environment is air, and electric current is automatic, and matrix effect is not consider.The each method of energy dispersion type x-ray fluorescence spectrophotometer
Parameter is as shown in table 2.
Table 2:
Cu mass percent concentration after 2c) being converted with table 1 is started sample introduction one by one for initial data and adopts spectrum, each sample introduction
Sample liquid thickness be 15mm, record the fluorescence intensity of the cu of each sample introduction, with the mass percent concentration of cu in each copper working solution
For abscissa, with fluorescence intensity corresponding with the mass percent concentration of above-mentioned cu as vertical coordinate, make calibration curve, such as Fig. 1
Shown.
Embodiment 2
Controlled trial fireworks and firecrackers basic copper carbonate reference material being measured using the method for the invention:
Tested with listed reference material in table 3, the copper nominal content of wherein reference material is as shown in table 3；Using
When the method for the invention measures, reference material carries out copper content testing after preparing test liquid as follows again.
1) prepare test liquid:
Test liquid is prepared for sample with the reference material of numbering 1, weighs 3 parts of 0.29g～0.31g sample, accurate when weighing
To 0.1mg, the 1st part of sample is placed in 300ml beaker, and presses the amount addition nitric acid of 60ml/g～80ml/g sample, places electric furnace
Upper heating micro-boiling 25min～30min, uses filter paper filtering while hot, and filtrate collection to volumetric flask treats the solution cooling in volumetric flask
Add water to room temperature and be settled to certain volume, obtain the 1st part of test liquid.Wherein, the mass percent concentration of nitric acid be 40%～
60% mass.Repeat said method, obtain 3 parts of test liquids of No. 1 reference material.
2) Cupper determination 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 display on grapher, the calibration song being determined according to embodiment 1 with this fluorescence intensity
Line reads corresponding cu mass percent concentration value；
Then as follows calculate numbering 1 reference material in copper mass percent concentration:
Wherein, ω represents the mass percent concentration of copper in sample, and unit is %；ω0Represent and read according to calibration curve
Cu mass percent concentration value, unit be %；2 represent the sample size that calibration curve supposes, unit is g；M represents that sample is actual
The quality weighing, unit is g；V represents the volume of actual constant volume after sample dissolution, and unit is ml it is ensured that in solution after constant volume
The concentration of cu is in calibration curve scope；500 represent the volume supposing sample size constant volume, and unit is ml.
Take wherein three result of calculation values meansigma methodss be numbering 1 reference material copper content, 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, respectively prepare numbering 2～8 reference material test liquid, calculate it
Copper content and the response rate, the results are shown in Table 3.
Table 3:
As shown in Table 3, the method for the invention is surveyed to copper in the fireworks and firecrackers basic copper carbonate of different main contents
Surely there is good accuracy.
Embodiment 3
Precision test using the testing result to reference material for the method for the invention:
Tested with the main content basic copper carbonate reference material of three differences for sample in the present embodiment, numbering is 1,2
With 3.
1) prepare test liquid:
Test liquid is prepared for sample with the reference material of numbering 1, weighs 4 parts of 0.29g～0.31g sample, accurate when weighing
To 0.1mg, the 1st part of sample is placed in 300ml beaker, and presses the amount addition nitric acid of 60ml/g～80ml/g sample, places electric furnace
Upper heating micro-boiling 25min～30min, uses filter paper filtering while hot, and filtrate collection to volumetric flask treats the solution cooling in volumetric flask
Add water to room temperature and be settled to certain volume, obtain the 1st part of test liquid.Wherein, the mass percent concentration of nitric acid be 40%～
60% mass.Repeat said method, obtain 4 parts of test liquids of No. 1 reference material.
2) in reference material copper content mensure:
By embodiment 1 step 2b) testing conditions, by 4 parts of test liquid sample introductions one by one of the reference material of numbering 1, every part
Test liquid measures 11 times, and it is 15mm that each sample introduction makes sample liquid thickness, and the fluorescence intensity of display on grapher, with this fluorescence intensity
Corresponding cu mass percent concentration value is read according to the calibration curve that embodiment 1 determines；
Then calculate the mass percent concentration of copper in the reference material of numbering 1 as follows, result is as shown in table 4.
Wherein, ω represents the mass percent concentration of copper in sample, and unit is %；ω0Represent and read according to calibration curve
Cu mass percent concentration value, unit be %；2 represent the sample size that calibration curve supposes, unit is g；M represents that sample is actual
The quality weighing, unit is g；V represents the volume of actual constant volume after sample dissolution, and unit is ml it is ensured that in solution after constant volume
The concentration of cu is in calibration curve scope；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 the reference material of numbering 2 and 3 respectively, and calculate
Their copper content, the results are shown in Table 4.
Table 4:
As shown in Table 4, the method for the invention in different main content basic copper carbonates copper measure have good
Precision, maximum allowable difference is 0.5%.
Embodiment 4
The mensure of copper content in actual fireworks and firecrackers basic copper carbonate:
1st, for the basic carbonate copper sample of detection:
1#: sample is derived from Guangxi Pubei County fireworks station-service in the basic copper carbonate raw material producing light pearl.
2#: sample is derived from Guangxi Lingshan County fireworks station-service in the basic copper carbonate former material producing display shell class effect medicine
Material.
2nd, using the method for the invention, above-mentioned basic carbonate copper sample is detected:
Because the calibration curve being determined using embodiment 1, therefore, the step for save drafting calibration curve, is directly carried out
Prepare the step that test liquid carries out upper machine mensure, specific as follows:
2.1) prepare test liquid:
Weigh 1# basic carbonate copper sample 0.29g～3 parts of 0.31g sample respectively, when weighing, be accurate to 0.1mg, the 1st part of examination
Sample is placed in 300ml beaker, by 60ml/g～80ml/g sample amount add nitric acid, place electric furnace on heating micro-boiling 25min～
30min, uses filter paper filtering, by filtrate collection to volumetric flask, add water after the solution in volumetric flask is cooled to room temperature constant volume while hot
To certain volume, obtain the 1st part of test liquid.Wherein, the mass percent concentration of nitric acid is 40%～60% mass.Repeat above-mentioned
Method, obtains 3 parts of test liquids of No. 1 reference material.
2.2) in basic copper carbonate copper content mensure:
By embodiment 1 step 2b) testing conditions, 3 parts of test liquid sample introductions one by one of 1# basic carbonate copper sample load
The sample path length of specimen cup is 15mm, and on grapher, the fluorescence intensity of display, is determined according to embodiment 1 with this fluorescence intensity
Calibration curve reads corresponding cu mass percent concentration value；
Then calculate the mass percent concentration of copper in 1# basic carbonate copper sample as follows, result is as shown in table 5.
Wherein, ω represents the mass percent concentration of copper in sample, and unit is %；ω0Represent and read according to calibration curve
Cu mass percent concentration value, unit be %；2 represent the sample size that calibration curve supposes, unit is g；M represents that sample is actual
The quality weighing, unit is g；V represents the volume of actual constant volume after sample dissolution, and unit is ml it is ensured that in solution after constant volume
The concentration of cu is in calibration curve scope；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# basic carbonate copper sample respectively, and calculate it
Copper content, the results are shown in Table 5.
While measuring above-mentioned basic carbonate copper sample with this method, it is also adopted by existing traditional chemical analysis side
Method (" fireworks and firecrackers mensure the 4th part of chemical raw material key index: basic copper carbonate " (sn/t 3056.4-
2011)) above-mentioned sample is detected, result is as described in Table 5.
Table 5:
As shown in Table 5, compared with existing chemical analysis method, accurately, deviation is little for measurement for the method for the invention.
Claims (9)
1. a kind of method measuring copper content in fireworks and firecrackers basic copper carbonate is it is characterised in that comprise the following steps:
1) draw calibration curve:
1.1) many parts of copper working solutions are prepared, the wherein mass concentration of cu controls in 0.10g/l～0.83g/l scope；
1.2) with energy dispersion type x-ray fluorescence spectrophotometer as detecting instrument, the sample size that supposed for calibration curve with 2.0g, adopt
Set up analysis method with the intensity correction method of x fluorescence spectrum quantitative analysis；By step 1.1) in many parts of copper working solutions preparing
The mass concentration of cu is converted into the mass percent concentration of cu, then sample introduction one by one, records the fluorescence intensity of the cu of each sample introduction,
The mass percent concentration of the cu with each copper working solution as abscissa, with fluorescence corresponding with the mass percent concentration of above-mentioned cu
Intensity is vertical coordinate, makes calibration curve；Wherein, by following formula, the mass concentration of cu in copper working solution is converted into cu's
Mass percent concentration:
Wherein, cu% represents the mass percent concentration of cu in copper working solution, and unit is %；C represents the matter of cu in copper 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) the quick copper content measuring in basic copper carbonate:
2.1) prepare test liquid: with basic copper carbonate as sample, when preparing test liquid, weigh a certain amount of sample, essence when weighing
Really arrive 0.1mg, be placed in beaker, add a certain amount of nitric acid, place and heat micro-boiling 25min～30min on electric furnace, use filter paper while hot
Filter, filtrate collection to volumetric flask adds water after the solution in volumetric flask is cooled to room temperature and is settled to certain volume；
2.2) press step 1.2) testing conditions, test liquid is loaded specimen cup it is ensured that sample liquid thickness >=15mm, on grapher
The fluorescence intensity of display, reads corresponding cu mass percent with this fluorescence intensity according to the calibration curve of above-mentioned determination dense
Angle value；
2.3) calculate sample in copper content:
As follows calculate sample in copper mass percent concentration:
Wherein, ω represents the mass percent concentration of copper in sample, and unit is %；ω0Represent the cu matter reading 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 represent actual constant volume after sample dissolution volume it is ensured that in solution after constant volume the concentration of cu bent in calibration
Line scope, unit is ml；500 represent the volume supposing sample size constant volume, and unit is ml.
2. according to claim 1 measure fireworks and firecrackers basic copper carbonate in copper content method it is characterised in that: described
Step 1.1) in, the method preparing copper working solution is: weigh a certain amount of high-purity cupric oxide powder or other copper reference materials,
Add appropriate nitric acid to be dissolved, after being settled to certain volume, obtain copper solution, then pipette the copper solution of different volumes respectively, use
Water obtains the copper working solution of variable concentrations after being settled to certain volume respectively；Wherein, the mass concentration of the cu of copper working solution controls
In 0.10g/l～0.83g/l scope.
3. according to claim 2 measure fireworks and firecrackers basic copper carbonate in copper content method it is characterised in that: described
Step 1.1) in, than for 40ml/g～60ml/g, the mass percent of nitric acid is dense for the volume mass of nitric acid and high-purity cupric oxide powder
Spend for 40%～60%.
4. according to claim 3 measure fireworks and firecrackers basic copper carbonate in copper content method it is characterised in that: described
Step 1.1) in, the mass percent concentration of nitric acid is 51%.
5. measure the method for copper content in fireworks and firecrackers basic copper carbonate according to claim 1 it is characterised in that described
Step 1.2) in, testing conditions are: using the x-ray light pipe collimator for 8.8mm～14mm for the aperture, can filter energy and be less than
The filter of the x-ray of 8.980kev, setting voltage be 16kv～24kv, analysis time be 30s～80s, energy range be 0～
40kev, during counting rate is, gaseous environment is air, and electric current is automatic, and matrix effect is not consider.
6. measure the method for copper content in fireworks and firecrackers basic copper carbonate according to claim 5 it is characterised in that described
Step 1.2) in, testing conditions are: using the x-ray light pipe collimator for 8.8mm for the aperture, setting filter is middle pd, setting electricity
Press as 20kv, analysis time is 50s, energy range is 0～20kev.
7. according to claim 1 measure fireworks and firecrackers basic copper carbonate in copper content method it is characterised in that: described
Step 2.1) in, the amount of weighing of sample is 0.29g～0.31g.
8. according to claim 1 measure fireworks and firecrackers basic copper carbonate in copper content method it is characterised in that: described
Step 2.1) in, nitric acid is added by the amount of 60ml/g～80ml/g sample, and the mass percent concentration of nitric acid is 40%～
60%.
9. according to claim 1 measure fireworks and firecrackers basic copper carbonate in copper content method it is characterised in that: described
Step 2.2) in, sample liquid thickness is 15mm～30mm.
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