CN107478595A - The method that a kind of the quick discriminating pearl powder true and false and quantitative forecast mix pseudo- shell powder content - Google Patents
The method that a kind of the quick discriminating pearl powder true and false and quantitative forecast mix pseudo- shell powder content Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 102
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000000203 mixture Substances 0.000 title claims abstract description 12
- 238000001228 spectrum Methods 0.000 claims abstract description 38
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000005259 measurement Methods 0.000 claims abstract description 4
- 238000003672 processing method Methods 0.000 claims abstract description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 48
- 241000276489 Merlangius merlangus Species 0.000 claims description 45
- 238000002329 infrared spectrum Methods 0.000 claims description 20
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 18
- 238000012360 testing method Methods 0.000 claims description 14
- 230000001360 synchronised effect Effects 0.000 claims description 12
- 238000004458 analytical method Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 230000004069 differentiation Effects 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 230000009466 transformation Effects 0.000 claims description 4
- 238000005452 bending Methods 0.000 claims description 3
- 238000010835 comparative analysis Methods 0.000 claims description 3
- 230000001186 cumulative effect Effects 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 238000011017 operating method Methods 0.000 claims description 2
- 239000000835 fiber Substances 0.000 abstract description 4
- 238000004476 mid-IR spectroscopy Methods 0.000 abstract description 4
- 238000004611 spectroscopical analysis Methods 0.000 abstract description 4
- 238000001514 detection method Methods 0.000 description 5
- 238000012850 discrimination method Methods 0.000 description 4
- 238000007689 inspection Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 235000015170 shellfish Nutrition 0.000 description 3
- 241001269238 Data Species 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000004971 IR microspectroscopy Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 238000004497 NIR spectroscopy Methods 0.000 description 1
- 238000000692 Student's t-test Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
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- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
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Abstract
The method that a kind of the quick discriminating pearl powder true and false and quantitative forecast mix pseudo- shell powder content, it is characterised in that:The infrared Rapid identification system of the incremental three-level of resolution capability is established using FT-mid-IR fiber optics spectroscopy, pass through the apparent resolution of enhanced spectrum step by step, the characteristic fingerprint band of true and false pearl powder can be identified so as to improve the fingerprint characteristic of collection of illustrative plates and obtain, passes through the true and false of the direct Qualitative Identification pearl powder of spectrum difference;And establish Quantitative Prediction Model with reference to Chemical Measurement processing method PLS, reach it is quick, lossless, accurate, the shell powder content that is doped in pearl powder is effectively estimated.
Description
Technical field
Differentiate the present invention relates to a kind of with the pearl of jib shellfish cultivation and with the oyster shell whiting mixed powder of its grinding shells
Discrimination method, the method that especially a kind of the quick discriminating pearl powder true and false and quantitative forecast mix pseudo- shell powder content.
Background technology
Pearl powder be clean, fine powder of the dried pearl after mechanical force is ground, oyster shell whiting be remove pearl
The cuticula of shell, the powder obtained by after mechanical force is ground.Pearl powder is a kind of important medicine and cosmetic material, and shellfish
The microscopic appearance and chemical constituent of shell powder have suitable similitude with pearl powder;In view of pearl powder has higher economic valency
Value, so that the phenomenon sold in pearl powder is pretended to be or be doped in the common oyster shell whiting with low cost in pearl powder selling market.
Above-mentioned fraud largely dampened consumption demand and the purchase confidence of consumer, very disruptive pearl powder industry
Benign competition, hinder the sustainable and healthy development in pearl powder market.Therefore, the pearl powder of artificial culture and its shellfish how to be solved
The true and false of shell grinding powder, which differentiates, just turns into the technical task that quality inspection worker urgently wishes to solve.For this many research unit
Inventor has done and much probed into around solving this problem.Chinese patent literature discloses the solution pearl that many inventors propose
Powder and the discrimination method for being entrained in oyster shell whiting in pearl powder.
Wherein:Patent No. ZL200910099718.X " a kind of discrimination method of pearl powder and oyster shell whiting " is by pearl powder
After being calcined with oyster shell whiting, diascope is mixed and made into KBr respectively, then in 400-4000cm-1Under the conditions of determine it
Infrared spectrum, pearl powder and oyster shell whiting are distinguished according to its characteristic peak at several specific bands.
Patent No. ZL201310373325.X is proposed " near infrared spectrum identification method that pearl powder mixes puppet ";The patent No.
Proposed " the near infrared spectrum qualitative identification method of pearl powder and oyster shell whiting " for 201310372853.3;Application No.
A kind of 201110121080.2 methods that pearl powder quality is analyzed using XRD diffraction approaches proposed;Patent No.
201310198751.4 propose be using Fourier transform infrared spectroscopy and whiteness test GC-MS differentiate pearl powder with
The method of oyster shell whiting;The technical scheme that Patent No. ZL201310251870.1 is proposed is differentiated using infrared microscopy reflectance spectrum
The technology of pearl powder and oyster shell whiting.
These above-mentioned pearl powder distinguishing method between true and false, have microscopical characters method, X-ray diffraction method, physical and chemical reaction differential method and
Thermal analysis system etc., these methods are mainly with the species and content difference of microstructure appearance, the difference of the hot phase transformation of powder or organic matter
Deng being used as differentiation foundation, these distinguishing rules have some limitations or error resistance and detection process wastes time and energy, and consumption is big
Measure chemical reagent.And pearl powder false distinguishing method common in recent years is mostly near infrared spectroscopy, though compared to other method method tool
There is the advantage such as easy, quick, lossless, but near-infrared spectrum technique must be realized to unknown sample by establishing calibration model
Analysis, absorption signal is weaker, bands of a spectrum are more and overlapped, and information parsing is difficult;More importantly in some above-mentioned discrimination methods
In, many methods must be heated or calcined to sample, can not veritably be reached quick and be obtained testing result;Actually using
In there is certain limitation.
Therefore, how to solve to realizing quick detection doped with the pearl powder of oyster shell whiting, and can determine that shell in pearl powder
The content of powder is still the technical task that the industry is badly in need of solving.
The content of the invention
The purpose of the present invention:It is directed to one kind and is different from that pearl powder is detected and determined using infrared spectrum, and pearl
The method for quick identification of oyster shell whiting in powder.
The method that this quick discriminating pearl powder true and false and quantitative forecast mix pseudo- shell powder content, it is characterised in that:Utilize
FT-mid-IR fiber optics spectroscopy establishes the infrared Rapid identification system of the incremental three-level of resolution capability, passes through enhanced spectrum step by step
Apparent resolution, the characteristic fingerprint band of true and false pearl powder can be identified so as to improve the fingerprint characteristic of collection of illustrative plates and obtain, is passed through
The true and false of the direct Qualitative Identification pearl powder of spectrum difference;And established with reference to Chemical Measurement processing method PLS quantitative pre-
Survey model, reach it is quick, lossless, accurate, the shell powder content that is doped in pearl powder is effectively estimated.
Specifically include following four operating procedure:
(1) collection of infrared spectrum;
(2) collection of the synchronous correlation spectrum of two dimension;
(3) characteristic fingerprint band is extracted;
(4) foundation, assessment and the checking of quantitative model;
When carrying out the collection of infrared spectrum by step (1), the silent winged Buddhist nun high-tensile strength iS5 (Thermo of U.S.'s match are utilized
Scientific Nicolet iS5) Fourier transformation infrared spectrometer gathers pure pearl powder, pure oyster shell whiting and doping respectively
The infrared spectrum for mixing pseudo- pearl powder sample of the oyster shell whiting of 10%-90% mass fractions, S is designated as with pearl powder1, pure oyster shell whiting note
For S11, doping oyster shell whiting mass fraction is that 10%, 20% ... 100% sample is designated as S respectively2、S3…S10;
Test pattern, scanning range 4000-400cm are transmitted using pressing potassium bromide troche-1, scanning signal is cumulative 16 times, differentiates
Rate is ± 4cm-1, and obtain second dervative spectrogram using 13 multinomial least square methods are smooth.
When carrying out the collection of two-dimensional correlation spectra by step (2), pressing potassium bromide troche is loaded into alternating temperature annex, with temperature model
Enclose often to rise spectrum of 10 DEG C of collections between 30 DEG C to 120 DEG C;Pass through Two-dimensional Correlation Analysis software Nicolet
IN10SpectraCorr processing collections obtain two-dimentional synchronous spectrum figure.
Characteristic fingerprint band is extracted by step (3), passes through comparative analysis second dervative spectrogram correlation spectrum figure synchronous with two dimension
Characteristic peak difference, extraction is capable of the characteristic fingerprint band of qualitative differentiation;Pass through the second derivative spectrum graph discovery after Pretreated spectra:
Aragonite CO32-862cm-1The out-of-plane bending vibration υ at place2Band is in rule as the concentration of oyster shell whiting in pearl powder increases peak intensity
Property enhancing;830-880cm-1、690-725cm-1The synchronous related infrared spectrum of two dimension of wave band intuitively can enter to mixing pseudo- pearl powder
The qualitative differentiation of row, and 865cm-1Place is consistent with second derivative spectrum result to temperature-responsive law of force.
Foundation, assessment and the checking of quantitative model are carried out according to step (4):The known doping oyster shell whiting mass fraction of collection exists
0th, the original infrared spectrum of 10%, 20% ... 100% 66 testing samples, wherein the data of 43 samples establish calibration set,
15 sample datas establish checking collection, and ratio is close to 3:1;Second dervative spectrogram is smoothly obtained using 13 points, uses polynary scattering
Correction method (MSC) establishes PLS quantitative models, wave band chooses 857- to Pretreated spectra using TQ Analyst9.0 analysis softwares
893cm-1Scope.
Gained modeling result is that the coefficient correlation of calibration set is 0.9820, and calibration set root-mean-square error (RMSEC) value is
5.69;The coefficient correlation of checking collection is 0.9866, and forecast set root-mean-square error (RMSEP) value is 4.62.T is examined and is also known as
Student t examine (Student's t test):For testing model applicability, oyster shell whiting mass fraction is prepared respectively and is existed
25%th, 55%, 85% pseudo- pearl powder sample (being labeled as sample A, B, C) of mixing is tested, and every kind of sample determines six times.
Acquired results look into t distribution tables:F=n1+n2During -2=10, if α=0.05, t0.05 10=1.812.tA、tB、tCValue
Respectively less than t0.05 10, i.e., significant difference is not present in infrared analysis A, B, C sample between the content value of oyster shell whiting and actual value,
When carrying out t inspections, it is in inspection level to look into t distribution tables:α=0.05, confidence level 95%, when free degree f is 10, checked in
Numerical value.
Pseudo- shell powder content is mixed according to this quick discriminating pearl powder true and false and quantitative forecast that above technical scheme proposes
Method, compared with prior art with advantages below:
1st, this method establishes (the Fourier transform infrared spectroscopy combination of the infrared Rapid identification system of the incremental three-level of resolution capability
Second derivative spectrum and two-dimensional correlation spectra) fast qualitative identification is carried out to mixing pseudo- pearl powder, while partial least squares algorithm is based on,
Using FT-mid-IR fiber optics spectroscopy analytical technology (FT-MIR), by establishing calibration model to the shell that is mixed in pearl powder
Powder carries out quantitative analysis.
2nd, this method need to only gather sample infrared spectrum, without being broken to any physical heating processing of sample progress or chemistry
It is bad, other chemical reagent are not consumed in test process, simple testing process is quick, and whole process greatly improves within 8min
Detection efficiency, and do not form destruction to environment.
Brief description of the drawings
Fig. 1 is 4000-500cm-1Pure pearl powder (S1) and pure oyster shell whiting (S11) original infrared spectrogram under wave band;
Fig. 2 is 4000-500cm-1The original infrared spectrogram of pearl powder of different proportion oyster shell whiting is adulterated under wave band;
Fig. 3 is 1111-676cm-1The pearl powder second dervative infrared spectrogram of different proportion oyster shell whiting is adulterated under wave band;
Fig. 4 is 906-830cm-1The pearl powder part second derivative spectra figure of different proportion oyster shell whiting is adulterated under wave band;
Fig. 5 is 880-830,725-690cm-1Pure pearl powder (S1), 10% oyster shell whiting of doping (S2) and pure shell under wave band
The synchronous related infrared spectrogram of powder (S11) two dimension;
Fig. 6 is the PLS quantitative models to oyster shell whiting in pearl powder based on Fourier transform infrared spectroscopy.
Embodiment
The present invention is expanded on further below in conjunction with Figure of description, and provides embodiments of the invention.
The core of the detection method of the proposition of the present invention is:Resolution capability is established using FT-mid-IR fiber optics spectroscopy
The infrared Rapid identification system of incremental three-level, by the apparent resolution of enhanced spectrum step by step, so as to improve the fingerprint of collection of illustrative plates spy
Sign property simultaneously obtains the characteristic fingerprint band that can identify true and false pearl powder, passes through the direct Qualitative Identification pearl powder of spectrum difference
The true and false;And establish Quantitative Prediction Model with reference to Chemical Measurement processing method PLS, reach it is quick, lossless, accurate, pair
The shell powder content being doped in pearl powder is effectively estimated.
1. the collection of infrared spectrum:Utilize Thermo Scientific Nicolet iS5 FFIRs
Instrument gathers pure pearl powder, pure oyster shell whiting and doping different quality containing (distribution of 10%-90% scopes inside gradient) oyster shell whiting and mixed
The infrared spectrum of pseudo- pearl powder sample, pure pearl powder are designated as S1, and pure oyster shell whiting is designated as S11, and doping oyster shell whiting mass fraction is
10%th, 20% ... 100% sample is designated as S2, S3 respectively ... S10.
KBr and powder to be measured blending grinding (are pressed into by transparent sheet, powder to be measured and KBr mass using pressing potassium bromide troche
Than for 1:100) test pattern, scanning range 4000-400cm, are transmitted-1, scanning signal is cumulative 16 times, and resolution ratio is ± 4cm-1。
Second dervative spectrogram is obtained using 13 multinomial least square methods are smooth.
2. the collection of two-dimensional correlation spectra:Same pressing potassium bromide troche, load alternating temperature annex, being 30 DEG C in temperature range arrives
Often rise spectrum of 10 DEG C of collections between 120 DEG C.At Two-dimensional Correlation Analysis software NicoletiN10SpectraCorr
Reason collection obtains two-dimensional correlation spectrogram.
3. extract characteristic fingerprint band:Pass through the characteristic peak of comparative analysis second derivative spectrum correlation spectrum spectrogram synchronous with two dimension
The characteristic fingerprint band of qualitative differentiation is capable of in difference, extraction.Aragonite CO3 is had found by the second derivative spectrum after Pretreated spectra2-'s
862cm-1The out-of-plane bending vibration υ at place2Band strengthens with the concentration increase peak intensity of oyster shell whiting in pearl powder in regular.830-
880cm-1、690-725cm-1The synchronous related infrared spectrum of two dimension of wave band intuitively can carry out qualitative differentiation to mixing pseudo- pearl powder,
And 865cm-1Place is consistent with second derivative spectrum result to temperature-responsive law of force.
4. the foundation of quantitative model, assessment and checking:The known doping oyster shell whiting mass fraction of collection is 0,10%, 20% ...
The original infrared spectrum of 100% 66 testing samples, wherein the data of 43 samples establish calibration set, 15 sample datas are built
Vertical checking collection, ratio is close to 3:1.Second dervative spectrogram is smoothly obtained using 13 points, using multiplicative scatter correction method (MSC) to light
Spectrum pretreatment, PLS quantitative models are established using the analysis softwares of TQ Analyst 9.0, wave band chooses 857-893cm-1Scope.
Gained modeling result is that the coefficient correlation of calibration set is 0.9820, and calibration set root-mean-square error (RMSEC) value is
5.69;The coefficient correlation of checking collection is 0.9866, and forecast set root-mean-square error (RMSEP) value is 4.62.T is examined:To examine mould
Type applicability, respectively prepare oyster shell whiting mass fraction 25%, 55%, 85% mix pseudo- pearl powder sample (labeled as sample A,
B, C) to be tested, every kind of sample determines six times.Acquired results look into t distribution tables:F=n1+n2During -2=10, if α=0.05,
t0.05 10=1.812.tA、tB、tCValue is respectively less than t0.05 10, i.e., the content value and actual value of oyster shell whiting in infrared analysis A, B, C sample
Between be not present significant difference (t examine when, it is in inspection level to look into t distribution tables:α=0.05, confidence level 95%, freely
When to spend f be 10, the numerical value that is checked in).Show the oyster shell whiting doping ratio based on PLS methods structure in the quantitative pre- of 10%-100%
It is good to survey modelling effect, accurately can quickly determine pearl powder and mix pseudo- content range, and can be used for actual production.
Table 1 is 880-830,725-690cm-1Pure pearl powder (S1), 10% oyster shell whiting of doping (S2) and pure shell under wave band
The synchronous automatic peak of Two-Dimensional Correlation IR Spectroscopy of powder (S11);
(note plus " * " place represent to be strong automatic peak in wave-number range)
Table 2 is quantitative parameter of the detection model based on PLS of oyster shell whiting;
Table 3 is the accuracy test of shell powder content model in pearl powder
Above is the embodiments of the invention that the applicant provides according to basic intention, the whole of this intention is not represented,
The general improvement that any above-mentioned basic intention according to the present invention provides belongs to the protection category of the present invention.
Claims (4)
1. a kind of method that quick discriminating pearl powder true and false and quantitative forecast mix pseudo- shell powder content, it is characterised in that:Utilize Fu
In leaf transformation middle infrared spectrum establish the infrared Rapid identification system of the incremental three-level of resolution capability, pass through the table of enhanced spectrum step by step
Resolution ratio is seen, the characteristic fingerprint band of true and false pearl powder can be identified so as to improve the fingerprint characteristic of collection of illustrative plates and obtain, pass through ratio
To the true and false of the direct Qualitative Identification pearl powder of spectrum difference;And establish quantitative forecast with reference to Chemical Measurement processing method PLS
Model, reach it is quick, lossless, accurate, the shell powder content that is doped in pearl powder is effectively estimated.
2. the method that a kind of the quick discriminating pearl powder true and false and quantitative forecast as claimed in claim 1 mix pseudo- shell powder content,
It is characterized in that:Specifically include following four operating procedure:
(1) collection of infrared spectrum;
(2) collection of the synchronous correlation spectrum of two dimension;
(3) characteristic fingerprint band is extracted;
(4) foundation, assessment and the checking of quantitative model;
When carrying out the collection of infrared spectrum by step (1), the silent winged Buddhist nun's high-tensile strength iS5 Fourier transformation infrared spectrometers of U.S.'s match are utilized
Gather the oyster shell whiting of pure pearl powder, pure oyster shell whiting and doping 10%-90% mass fractions respectively mixes the red of pseudo- pearl powder sample
Outer spectrogram, S is designated as with pearl powder1, pure oyster shell whiting is designated as S11, doping oyster shell whiting mass fraction is 10%, 20% ... 100% sample
Product are designated as S respectively2、S3…S10;
Test pattern, scanning range 4000-400cm are transmitted using pressing potassium bromide troche-1, scanning signal is cumulative 16 times, and resolution ratio is
±4cm-1, and obtain second dervative spectrogram using 13 multinomial least square methods are smooth.
By step (2) carry out two-dimensional correlation spectra collection when, by pressing potassium bromide troche load alternating temperature annex, using temperature range as
Often rise spectrum of 10 DEG C of collections between 30 DEG C to 120 DEG C;Pass through Two-dimensional Correlation Analysis software Nicolet
IN10SpectraCorr processing collections obtain two-dimentional synchronous spectrum figure;
Characteristic fingerprint band is extracted by step (3), passes through the spy of comparative analysis second dervative spectrogram correlation spectrum figure synchronous with two dimension
Peak difference is levied, the characteristic fingerprint band of qualitative differentiation is capable of in extraction;Pass through the second derivative spectrum graph discovery after Pretreated spectra:Aragonite
CO3 2-862cm-1The out-of-plane bending vibration υ at place2Band increases with the concentration increase peak intensity of oyster shell whiting in pearl powder in regular
By force;830-880cm-1、690-725cm-1The synchronous related infrared spectrum of two dimension of wave band intuitively can be determined mixing pseudo- pearl powder
Property distinguish, and 865cm-1Place is consistent with second derivative spectrum result to temperature-responsive law of force;
Foundation, assessment and the checking of quantitative model are carried out by step (4):The known doping oyster shell whiting mass fraction of collection 0,
10%th, the original infrared spectrum of 20% ... 100% 66 testing samples, wherein the data of 43 samples establish calibration set, 15
Individual sample data establishes checking collection, and ratio is close to 3:1;Second dervative spectrogram is smoothly obtained using 13 points, uses polynary scattering school
(MSC) is executed to Pretreated spectra, establishes PLS quantitative models using the analysis softwares of TQ Analyst 9.0, wave band chooses 857-
893cm-1Scope.
3. a kind of the quick discriminating pearl powder true and false and quantitative forecast as described in right will require 1 and 2 mix pseudo- shell powder content
Method, it is characterised in that:Gained modeling result is that the coefficient correlation of calibration set is 0.9820, and calibration set root-mean-square error value is
5.69;The coefficient correlation of checking collection is 0.9866, and forecast set root-mean-square error value is 4.62.T is examined:It is applicable for testing model
Property, mix pseudo- pearl powder sample of the oyster shell whiting mass fraction 25%, 55%, 85% is prepared respectively, is carried out labeled as sample A, B, C
Test, every kind of sample determine six times.
4. a kind of the quick discriminating pearl powder true and false and quantitative forecast as described in right will require 1 and 2 mix pseudo- shell powder content
Method, it is characterised in that:Acquired results look into t distribution tables:F=n1+n2During -2=10, if α=0.05, t0.05 10=1.812;
tA、tB、tCValue is respectively less than t0.05 10, i.e., it is not present and shows between the content value of oyster shell whiting and actual value in infrared analysis A, B, C sample
Write sex differernce.
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