CN109596654A - The method of bromine antimony element in X fluorescence spectrum and infra-red sepectrometry combination measurement plastics - Google Patents
The method of bromine antimony element in X fluorescence spectrum and infra-red sepectrometry combination measurement plastics Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000005259 measurement Methods 0.000 title claims abstract description 41
- 229920003023 plastic Polymers 0.000 title claims abstract description 38
- 239000004033 plastic Substances 0.000 title claims abstract description 38
- LXWPJAGZRHTAOO-UHFFFAOYSA-N [Sb].[Br] Chemical compound [Sb].[Br] LXWPJAGZRHTAOO-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002189 fluorescence spectrum Methods 0.000 title claims abstract description 23
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 claims abstract description 65
- 125000001246 bromo group Chemical group Br* 0.000 claims abstract description 37
- 238000004566 IR spectroscopy Methods 0.000 claims abstract description 10
- 238000004846 x-ray emission Methods 0.000 claims abstract description 7
- 229910052787 antimony Inorganic materials 0.000 claims description 31
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 31
- 238000004519 manufacturing process Methods 0.000 claims description 24
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 21
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 19
- 229910052794 bromium Inorganic materials 0.000 claims description 19
- 238000012360 testing method Methods 0.000 claims description 19
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 17
- 239000003063 flame retardant Substances 0.000 claims description 15
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 230000004044 response Effects 0.000 claims description 10
- 238000004458 analytical method Methods 0.000 claims description 9
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 9
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 9
- 238000002329 infrared spectrum Methods 0.000 claims description 8
- 230000003595 spectral effect Effects 0.000 claims description 7
- 238000005453 pelletization Methods 0.000 claims description 4
- 238000001228 spectrum Methods 0.000 claims description 4
- GUSAMWMYRQHFMI-UHFFFAOYSA-N dioxoantimony Chemical group O=[Sb]=O GUSAMWMYRQHFMI-UHFFFAOYSA-N 0.000 claims description 3
- 238000001506 fluorescence spectroscopy Methods 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000001746 injection moulding Methods 0.000 claims 1
- 230000006378 damage Effects 0.000 abstract description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 11
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000009472 formulation Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004876 x-ray fluorescence Methods 0.000 description 4
- 238000005102 attenuated total reflection Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- -1 bromine flame retardant (brominated triazine Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002795 fluorescence method Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 241000692870 Inachis io Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000000120 microwave digestion Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 230000010076 replication Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- 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
- G01N23/22—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 by measuring secondary emission from the material
- G01N23/2202—Preparing specimens therefor
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3563—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing solids; Preparation of samples therefor
-
- G—PHYSICS
- G01—MEASURING; TESTING
- 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
- G01N23/22—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 by measuring secondary emission from the material
- G01N23/223—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 by measuring secondary emission from the material by irradiating the sample with X-rays or gamma-rays and by measuring X-ray fluorescence
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3563—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing solids; Preparation of samples therefor
- G01N2021/3572—Preparation of samples, e.g. salt matrices
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2201/00—Features of devices classified in G01N21/00
- G01N2201/06—Illumination; Optics
- G01N2201/068—Optics, miscellaneous
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/07—Investigating materials by wave or particle radiation secondary emission
- G01N2223/076—X-ray fluorescence
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/10—Different kinds of radiation or particles
- G01N2223/101—Different kinds of radiation or particles electromagnetic radiation
- G01N2223/1016—X-ray
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/60—Specific applications or type of materials
- G01N2223/623—Specific applications or type of materials plastics
Abstract
The present invention provides a kind of methods of bromine antimony element in X fluorescence spectrum and infra-red sepectrometry combination measurement plastics, after the content for measuring the bromo element and antimony element in plastics simultaneously including the use of x ray fluorescence spectrometry, infrared spectroscopy is recycled to measure the step of checking antimony element content.The method of bromine antimony element, can measure antimony element and bromo element, and antimony element measurement is accurate, measurement quickly, and does not damage sample simultaneously in X fluorescence spectrum of the present invention and infra-red sepectrometry combination measurement plastics.
Description
Technical field
The invention belongs to plastics detection fields, more particularly, to a kind of x ray fluorescence spectrometry and infrared spectroscopy
The method of bromo element in combination analysis ABS plastic, antimony element content.
Background technique
In ABS plastic flame-retardant system, to obtain better flame retardant effect, bromine antimony is mostly used to compound cooperative flame retardant.It is looking forward to
When industry produces bromine antimony flame-proof ABS plastic product, due to certain production technologies, it will cause above-mentioned flame-proof ABS plastics sometimes
Middle bromine antimony content changes, and the situation inconsistent with formula design flow occurs, and the content is directly related to flame retardant of plastic
Level influences the rank of plastic flame.Therefore it is particularly important to establish a kind of method for quickly measuring the plastics bromine antimony content, to
Monitor the production level and stability of product.
X fluorescence spectrum method is widely used in every field as a kind of quick, nondestructive analysis element means.Application
Also trial measures the bromine antimony element contents of bromine antimony flame-proof ABS plastics with this method to people, but there are some problems, i.e., antimony element excites
Intensity is weaker, and measurement result fluctuation is bigger, accuracy is undesirable.If using spectrophotometry, inductively coupled plasma
The chemical methodes such as body emission spectrum (ICP) method further measure antimony, and one side pre-treatment step is relatively cumbersome, it is many to need to consume
Chemical reagent, period are relatively long, are unable to satisfy the Quality Control requirement quickly analyzed；Another aspect sample can be destroyed, also not
It is able to achieve lossless test request.
Summary of the invention
In view of this, the present invention is directed to propose bromine antimony is first in a kind of X fluorescence spectrum and infra-red sepectrometry combination measurement plastics
The method of element can measure antimony element and bromo element with the defect of gram prior art simultaneously, and antimony element measurement is accurate, and measurement is fast
Speed, and do not damage sample.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:
The method of bromine antimony element in X fluorescence spectrum and infra-red sepectrometry combination measurement plastics, including the use of x-ray fluorescence light
After spectrometry measures the content of the bromo element and antimony element in plastics simultaneously, infrared spectroscopy measurement is recycled to check antimony element
The step of content.
Preferably, the method that x ray fluorescence spectrometry measures the content of bromo element and antimony element in plastics simultaneously includes
Following steps:
(1) preparation of X-fluorescence standard specimen sample: by plastics, bromine flame retardant, antimony oxide mixture through extruding pelletization,
It is molded into the circular slab of 2-6cm thickness, wherein the ratio of bromo element is 7-11wt%, and the ratio of antimony element is 0.5-5.0wt%；
(2) X-fluorescence experiment parameter determines: the analysis spectral line of selection Ka Kb choice of spectrum element, selection and spectral line phase
Corresponding angle；Voltage 30-50KV, electric current 40-300ua, time of measuring 100-300s, collimator 5mm, optical filter Cu
300um；
(3) foundation of X-fluorescence standard curve: intensity is carried out to bromo element and antimony element using Xray fluorescence spectrometer and is rung
The measurement that should be worth, establishes the relationship between corresponding element content and intensity response value, and drafting is modeled to opposite working curve；
(4) in actual production sample bromo element and antimony element measurement: to the sample of factory's actual production, carry out through squeezing out
It is granulated, the circular specimen with a thickness of 2-6cm is molded into, on identical Xray fluorescence spectrometer, using standard working curve to modeling
Bromo element, antimony element in material sample are analyzed.
Preferably, the plastics obtained in step (1) are the ABS plastic without bromo element and antimony element；Sample is in step (4)
Bromo element and the unknown ABS plastic of antimony element content.
Preferably, using infrared spectroscopy measure check antimony element content method the following steps are included:
(1) the infrared spectroscopy standard specimen sample containing antimony is prepared: by the mixture of plastics, bromine flame retardant, antimony oxide through squeezing
It is granulated out, is molded into the circular slab of 2-6cm thickness, wherein the ratio of antimony element is 0.5-5.0wt%；
(2) ATR Total Reflection Infrared attachment, scanning times 16-32 times, resolution ratio standard sample IR spectrum scanning: are used
1-4cm-1, when measurement, first carry out carrying out blank scanning to air, then, sample to be tested faced into quasi- test zone, is carried out infrared
Spectral scan, the infrared spectrogram of sample are the map that sample to be tested subtracts air blank；
(3) characteristic peak area is calculated, establishes working curve: 735cm-1For antimony in antimony oxide-oxygen functional group feature
Peak carries out auto-separating processing using device software, reads 720cm-1-750cm-1The peak area at place and according to this fitting operations are bent
Line；The working curve of fitting is y=4.1367x-1.04, and wherein y is characterized peak area, and x is antimony content；
(4) it tests the antimony content in production sample: reading 735cm in production sample-1Characteristic peak area, according to above-mentioned meter
Formula is calculated, the antimony content in sample can be directly gone out.
Preferably, the plastics in step (1) are the ABS plastic without bromo element and antimony element；Sample in step (4) is
The unknown ABS plastic of antimony element content, and the sample is identical as the sample to be tested in x ray fluorescence spectrometry.
Preferably, the bromine flame retardant is brominated triazine.
Preferably, in the mixture of plastics, bromine flame retardant, antimony oxide each component mass ratio are as follows: 78.9-88.4:
10.4-16.3:1.2-4.8.
The principle of the method for bromine antimony element is said in X fluorescence spectrum of the present invention and infra-red sepectrometry combination measurement plastics
It is bright:
(1) bromine antimony must measure simultaneously: because bromine antimony plays cooperative flame retardant effect, two kinds of elements must be obtained while be measured
Content cannot can only measure one of content.
(2) necessity associated with X fluorescence spectrum and infra-red sepectrometry: X-fluorescence measures bromine can be with, and measurement antimony is slightly worse, so
It must seek another way out and seek other test methods.The chemical method of general measure antimony, for example iodide colorimetric method, peacock green
Method, these methods often relate to the links such as extraction, colour developing, colorimetric, and consumption reagent multi-step is complicated, and the time is also grown.Again for example
It says, atomic absorption spectrum or atomic fluorescence method, these methods can also be related to long-term sour digestion process, can not realize fast
Speed, non-destructive determination.ICP method can only do antimony again, and bromine cannot be done.
(3) it for quick, lossless testing goal, introduces infrared spectrum determination method and measures antimony, using attenuated total reflectance
Method realizes lossless, quick accurate testing requirement, while can be fast and quasi- for making up X-fluorescence survey bromine, and it is fast but inaccurate to survey antimony
Defect and chemical method survey antimony standard but unhappy some disadvantages.
Compared with the existing technology, X fluorescence spectrum of the present invention and infra-red sepectrometry combination measure bromine antimony member in plastics
The method of element, has the advantage that
The method of bromine antimony element, glimmering by X in X fluorescence spectrum of the present invention and infra-red sepectrometry combination measurement plastics
Light method realizes the accurate analysis of bromine, antimony element, further uses infra-red sepectrometry and carries out more stable, accurate survey to antimony element
Examination, for conventional chemical accurate measurement method, in the result equally stablized, accurately tested, shortens the testing time, improves
Working efficiency.Furthermore it is possible to realize the flame retardant agent content quickly, nondestructively confirmed in ABS plastic, further guidance is practical raw
It produces, reduces the quantity of substandard product.
Detailed description of the invention
Fig. 1 is x-ray fluorescence method bromo element working curve in embodiment 1；
Fig. 2 is x-ray fluorescence method antimony element working curve in embodiment 1；
Fig. 3 is the infrared spectrogram of the standard items containing antimony in embodiment 1；
Fig. 4 is antimony oxide 735cm in embodiment 1-1The infrared spectrogram at place；
Fig. 5 is 735cm in embodiment 1-1Peak area working curve.
Specific embodiment
In addition to being defined, technical term used in following embodiment has universal with those skilled in the art of the invention
The identical meanings of understanding.Test reagent used in following embodiment is unless otherwise specified conventional biochemical reagent；It is described
Experimental method is unless otherwise specified conventional method.
Below with reference to examples and drawings, the present invention will be described in detail.
Standard sample used in X fluorescence spectrum and infra-red sepectrometry test antimony element is identical in embodiment 1, embodiment 1, right
Ratio 1 is identical with the test standard sample in comparative example 2, and production sample is also identical.
Embodiment 1
The method of bromine antimony element content in X fluorescence spectrum and infra-red sepectrometry combination measurement ABS plastic:
1. preliminary bromo element, antimony element analysis first are carried out to bromine, antimony flame-proof ABS plastics using x ray fluorescence spectrometry,
Step includes:
(1) prepared by X-fluorescence standard sample: according to ratio described in table 1, by without bromo element and antimony element ABS plastic (
That is blank plastic), bromine flame retardant (brominated triazine, bromo element content 67.4wt%), antimony oxide (antimony element content
Mixture 83.5wt%) is molded into the circular slab of 4cm thickness through extruding pelletization.
1 X-fluorescence standard sample ratio table of table
(2) X fluorescence spectrometer device parameter determines:
Screened by a large number of experiments, experimental condition parameter is, bromo element, antimony element analysis spectral line be Ka；Bromo element
Analytic angle be 13.402 °, the analytic angle of antimony element is 29.955 °；Voltage 40KV, electric current 200ua, time of measuring
200s, collimator 5mm, optical filter Cu 300um.
(3) foundation of X-fluorescence standard curve:
X-fluorescence measurement is carried out to standard sample, the intensity response value of two kinds of bromine, antimony elements is measured respectively, establishes response
With the relationship of content.Fig. 1 and Fig. 2 is respectively the working curve that bromine and antimony element are established according to content and intensity response value, in which:
It is y=397.86x-5.2043 that X-fluorescence, which calculates bromine matched curve, and x is the content of bromo element in formula, and y is intensity response value；X
It is y=434.2x+291 that fluorescence, which calculates antimony matched curve, and x is the content of antimony element in formula, and y is intensity response value.X-fluorescence mark
Bromo element and antimony element sample ratio and its corresponding intensity response value are shown in Table 2 in quasi- sample.
Bromo element and antimony element sample ratio and its corresponding intensity response value in 2 X-fluorescence standard sample of table
(4) actual production sample X-fluorescence measures:
Actual production sample of pellets on production line (actual content of bromo element and antimony element is unknown) is taken, through being molded into thickness
The circular specimen progress X fluorescence spectrum test that degree is 4cm, replication 10 times.Known to the theoretical additive amount of the sample (namely it is real
Border production sample of pellets production when its each component theoretical formulation content be it is certain, calculated according to formulation content
The content of theoretical bromine and antimony element is known).Table 3 the result shows that, bromo element measure relative standard deviation 3.6%, relatively partially
Poor 3.4%, illustrate that measurement reproducibility and accuracy are preferable.Antimony element relative standard deviation 10.2%, relative deviation 13.5%,
Repeatability and accuracy are all larger than 10%, measure fluctuation and accuracy is slightly worse than bromo element.
3 production sample X-fluorescence test result of table
2, to the antimony element further progress examination of infrared spectrum in above-mentioned ABS plastic, step includes:
(1) the infrared spectroscopy standard specimen sample containing antimony is prepared
The standard items of ABS plastic containing antimony for establishing working curve are prepared, namely: it will be without bromo element and antimony element
ABS plastic (namely blank plastic), bromine flame retardant (brominated triazine, bromo element content 67.4wt%), antimony oxide (antimony element
Content 83.5wt%) mixture through extruding pelletization, be molded into the circular slab of 4cm thickness；Antimony element content 0.5-4.0wt%, contains
Measuring spacing gradient is 0.5%.
(2) sample IR spectrum scanning
Using attenuated total reflectance attachment ATR, crystalline material is diamond, can be directly realized by lossless point of the surface of solids
Analysis.Selection scanning times 32 times, resolution ratio 4cm-1.When measurement, only by the smooth face-down alignment test zone of sample, carry out
IR spectrum scanning.Carry out first to air carry out blank scanning, be then scanned to sample to be tested, sample it is red
External spectrum figure is the map that sample to be tested subtracts air blank.1 sample test about 1min.
(3) characteristic peak area is calculated, working curve is established
735cm-1For antimony in antimony oxide-oxygen functional group characteristic peak, because of 735cm-1With it is single-substituted in ABS
Characteristic peak 760cm-1There is overlapping at peak, more accurately to calculate peak area, therefore is carried out at auto-separating using equipment corresponding software
Reason reads 720cm-1~750cm-1The peak area at place.Fig. 5 is 735cm-1The working curve of characteristic peak area and antimony element, fitting
Working curve be y=4.1367x-1.04, wherein y is characterized peak area, and x is antimony content.Read 735cm in production sample-1
Characteristic peak area can directly go out the antimony content in sample according to above-mentioned calculation formula.
(4) the infra-red sepectrometry antimony content test in actual sample
Choose the actual production sample (actual content of bromo element and antimony element is unknown) of different antimony contents, real content
It is known (namely each sample of actual production production when its each component theoretical formulation content be it is certain, according to formulation content
The content of the theoretical antimony element calculated is known), carry out examination of infrared spectrum quantitative analysis.Each sample measurement 10
It is secondary.Table 4 is the result that sample mid-infrared light spectrometry measures antimony element.
4 production sample antimony element infrared spectrum measurement result of table
Comparative example 1 --- X-fluorescence method comparative example
X-ray fluorescence spectra quantitative analysis control is also carried out to above-mentioned sample.Table 5 is X fluorescence spectrum method measurement in sample
The result of antimony element.As can be seen from Table 5, the fluctuation of X-fluorescence measurement antimony is bigger, relative standard deviation 9.76%-
11.98%；And then accuracy is not very good, the relative deviation for measuring antimony is 5.0%-11.5%.
5 production sample antimony element X fluorescence spectrum method measurement result of table
Comparative example 2 --- ICP method comparative example
Carry out ICP method quantitative analysis also to above-mentioned sample to compare.Table 6 is the knot that ICP method measures antimony element in sample
Fruit.
Pre-treatment step: 0.2g sample is weighed as in micro-wave diminishing pot, 6ml concentrated nitric acid, 1ml concentrated hydrochloric acid is added, carries out
Micro-wave digestion.Resolution condition are as follows: from 0w to 400w, climb time 15min, keeps 10min；700w is raised to from 400w, when climbing
Between 15min, keep 40min；50 DEG C, about 40min are cooled to, resolution terminates.After being fully cooled, it is fixed to pour into volume in volumetric flask
Hold to 100ml, filtering.Entire pre-treatment step needs 2.5h or so.
Upper machine step: selection antimony spectral line first carries out concentration curve foundation, then carries out 10 repeatability measurements.
Based on the above embodiments and comparative example, from table 4- table 6 as can be seen that whether repeatability or accuracy, X are glimmering
The effect of light measurement antimony element is worst.
Compare infra-red sepectrometry and ICP method again, ICP method relative standard deviation is 2.25%-5.51%, relative deviation
0.4%-1.7%；The relative standard deviation of infra-red sepectrometry is 3.59%-5.55%, relative deviation 1.6%-2.0%.The two
Repeatability be it is relatively good, relative standard deviation RSD can achieve 5% or so；The accuracy of the two is also to compare simultaneously
Alright, relative deviation can be lower than 5%, substantially meet the demand of existing test.
Under the requirement for reaching essentially identical test accuracy and precision, the time that infra-red sepectrometry tests antimony element is big
Big to shorten, 1 sample only needs 1min, eliminates the resolution step and corresponding heating, cooling time of ICP method, be also not used
Any reagent, saving time several hours, saving reagent are several.
Meanwhile unlike ICP method clears up destruction sample completely, also unlike other conventional infra-red sepectrometry such as potassium bromide
Pressed disc method, pressure sintering or coating method can equally destroy sample, and lossless survey is realized using attenuated total reflectance infra-red sepectrometry
Examination requires, and does not carry out any processing to sample, can directly be directly realized by the nondestructive analysis of the surface of solids.
6 production sample antimony element ICP method measurement result of table
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (7)
- The method of bromine antimony element in 1.X fluorescence spectrum and infra-red sepectrometry combination measurement plastics, it is characterised in that: including the use of X After ray fluorescence spectrometry measures the content of the bromo element and antimony element in plastics simultaneously, infrared spectroscopy measurement is recycled The step of checking antimony element content.
- 2. the method for bromine antimony element in X fluorescence spectrum according to claim 1 and infra-red sepectrometry combination measurement plastics, It is characterized in that: the x ray fluorescence spectrometry while method for measuring the content of the bromo element in plastics and antimony element includes following step It is rapid:(1) preparation of X-fluorescence standard specimen sample: by plastics, bromine flame retardant, antimony oxide mixture through extruding pelletization, injection molding At the circular slab of 2-6cm thickness, wherein the ratio of bromo element is 7-11wt%, and the ratio of antimony element is 0.5-5.0wt%；(2) X-fluorescence experiment parameter determines: the analysis spectral line of selection Ka Kb choice of spectrum element selects corresponding with spectral line Angle；Voltage 30-50KV, electric current 40-300ua, time of measuring 100-300s, collimator 5mm, optical filter Cu 300um；(3) intensity response value the foundation of X-fluorescence standard curve: is carried out to bromo element and antimony element using Xray fluorescence spectrometer Measurement, establish the relationship between corresponding element content and intensity response value, drafting is modeled to opposite working curve；(4) in actual production sample bromo element and antimony element measurement: to the sample of factory's actual production, make through squeezing out Grain, is molded into the circular specimen with a thickness of 2-6cm, on identical Xray fluorescence spectrometer, using standard working curve to plastics Bromo element, antimony element in sample are analyzed.
- 3. the method for bromine antimony element in X fluorescence spectrum according to claim 2 and infra-red sepectrometry combination measurement plastics, Be characterized in that: it is the ABS plastic without bromo element and antimony element that plastics are obtained in step (1)；In step (4) sample be bromo element and The unknown ABS plastic of antimony element content.
- 4. the method for bromine antimony element in X fluorescence spectrum according to claim 1 and infra-red sepectrometry combination measurement plastics, Be characterized in that: using infrared spectroscopy measure check antimony element content method the following steps are included:(1) it prepares the infrared spectroscopy standard specimen sample containing antimony: the mixture of plastics, bromine flame retardant, antimony oxide is made through squeezing out Grain, is molded into the circular slab of 2-6cm thickness, and wherein the ratio of antimony element is 0.5-5.0wt%；(2) ATR Total Reflection Infrared attachment, scanning times 16-32 times, resolution ratio 1-4cm standard sample IR spectrum scanning: are used-1, when measurement, first carry out carrying out blank scanning to air, then, sample to be tested faced into quasi- test zone, carries out infrared spectroscopy Scanning, the infrared spectrogram of sample are the map that sample to be tested subtracts air blank；(3) characteristic peak area is calculated, establishes working curve: 735cm-1For antimony in antimony oxide-oxygen functional group characteristic peak, make Auto-separating processing is carried out with device software, reads 720cm-1-750cm-1The peak area at place and according to this fitting operations curve；It is quasi- The working curve of conjunction is y=4.1367x-1.04, and wherein y is characterized peak area, and x is antimony content；(4) it tests the antimony content in production sample: reading 735cm in production sample-1Characteristic peak area, it is public according to above-mentioned calculating Formula can directly go out the antimony content in sample.
- 5. the method for bromine antimony element in X fluorescence spectrum according to claim 4 and infra-red sepectrometry combination measurement plastics, Be characterized in that: the plastics in step (1) are the ABS plastic without bromo element and antimony element；Sample in step (4) is antimony element The unknown ABS plastic of content, and the sample is identical as the sample to be tested in x ray fluorescence spectrometry.
- 6. the side of bromine antimony element in X fluorescence spectrum according to claim 2 or 4 and infra-red sepectrometry combination measurement plastics Method, it is characterised in that: the bromine flame retardant is brominated triazine.
- 7. the side of bromine antimony element in X fluorescence spectrum according to claim 2 or 4 and infra-red sepectrometry combination measurement plastics Method, it is characterised in that: plastics, bromine flame retardant, antimony oxide mixture in each component mass ratio are as follows: 78.9-88.4: 10.4-16.3:1.2-4.8.
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