Summary of the invention
Fundamental purpose of the present invention is to provide a kind of perfluoroisopropyl hexanone fire extinguishing agent recognition detection method, is intended to fill the domestic blank to perfluoroisopropyl hexanone fire extinguishing agent recognition detection method.
For achieving the above object, a kind of perfluoroisopropyl hexanone fire extinguishing agent recognition detection method provided by the invention, comprises the following steps:
Step one, mensuration testing sample are 4050cm to wave-number range
-1~ 5323cm
-1the absorption spectrum of near infrared light, the wave number of absorption peak and absorbance;
Step 2, detection testing sample are 4065.2cm in wave number
-1(± 5cm
-1), 4670.8cm
-1(± 5cm
-1), 4790.3cm
-1(± 5cm
-1), 5280.1cm
-1(± 5cm
-1) whether place all have absorption peak, if do not had, then judge to treat that test sample is as non-perfluorinated isopropyl hexanone fire extinguishing agent; If had, then enter next step and continue to detect;
Step 3, second order differentiate pre-service is carried out to the absorption spectrum of testing sample after, obtain the pre-processed spectrum of testing sample, and be 4049.8cm according to this spectrum in wave number section
-1~ 4998.6cm
-1and 5237.7cm
-1~ 5322.6cm
-1corresponding derivative value sets up Euclidean distance model, similarity coefficient model or consistency check model;
Step 4, by the calculated value of described Euclidean distance model, similarity coefficient model or consistency check model with preset detection limit contrast, the value calculated when described Euclidean distance model and described similarity coefficient model is not less than default detection limit, then judge testing sample whether perfluoroisopropyl hexanone fire extinguishing agent, otherwise judge that testing sample is as non-perfluorinated isopropyl hexanone fire extinguishing agent;
When the value that described consistency check model calculates is less than default detection limit, then judge that testing sample is as perfluoroisopropyl hexanone fire extinguishing agent, otherwise judge that testing sample is as non-perfluorinated isopropyl hexanone fire extinguishing agent.
Preferably, described Euclidean distance model is:
Wherein, i be [1 ,+∞) in natural number, x
ifor the derivative value that i-th wave number in the wave number section in step 3 is corresponding, s
ifor the derivative value that i-th wave number is corresponding in described wave number section of perfluoroisopropyl hexanone in step 3;
Definition x
ieuclidean distance value corresponding when=0 gets maximal value D
max; Definition x
i=s
itime, corresponding Euclidean distance value gets minimum value D
min; By D
maxand D
mingeometric ratio is linearly converted into the matching value between 0 ~ 100, if when the matching value calculated is not less than detection limit 95, then judges that testing sample is as perfluoroisopropyl hexanone fire extinguishing agent, otherwise is judged to be non-perfluorinated isopropyl hexanone fire extinguishing agent.
Preferably, described similarity coefficient model is:
Wherein, R ∈ [-1,1], i ∈ [1 ,+∞) in natural number, x
ifor the derivative value that i-th beam location in the wave number section in step 3 is corresponding, s
ioriginal spectrum for perfluoroisopropyl hexanone carries out the pretreated spectrum of the second order differentiate derivative value that i-th wave number is corresponding in described wave number section,
for the mean value of the derivative value of testing sample in described wave number section;
original spectrum for perfluoroisopropyl hexanone carries out the mean value of the derivative value of the pretreated spectrum of second order differentiate in described wave number section;
When R ∈ [-1,0], represent that the near infrared spectrum similarity of testing sample and perfluoroisopropyl hexanone is 0%, when when R ∈ (0,1] time, the near infrared spectrum similarity of expression testing sample and perfluoroisopropyl hexanone is R
0∈ (0% ~ 100%] between corresponding number percent, work as R
0when being not less than detection limit 95%, then judging that testing sample is as perfluoroisopropyl hexanone fire extinguishing agent, otherwise be judged to be non-perfluorinated isopropyl hexanone fire extinguishing agent.
Preferably, described consistency check model is:
Wherein, i ∈ [1 ,+∞) in natural number, x
ifor the derivative value that i-th beam location in the described wave number section in step 3 is corresponding, the derivative value mean value that i-th beam location of perfluoroisopropyl hexanone in described wave number section repeatedly measures is
standard deviation is σ;
Work as CI
iwhen being less than detection limit 3, then judging that testing sample is as perfluoroisopropyl hexanone fire extinguishing agent, otherwise be judged to be non-perfluorinated isopropyl hexanone fire extinguishing agent.
Preferably, the method also comprised step 4 before step one: the standard model measuring perfluoroisopropyl hexanone is 4050cm to wave-number range
-1~ 5323cm
-1the absorption spectrum of near infrared light and the wave number of absorption peak;
Preferably, the standard model purity of described perfluoroisopropyl hexanone is greater than 99%.
Preferably, comprise carrying out second order differentiate pre-service to the absorption spectrum of testing sample: standard normal variable conversion is carried out to the original spectrum of testing sample and the second order differentiate of 5 level and smooth, five points difference width.
Preferably, be under constant temperature, testing sample is stored in quartz glass tube with liquid state to the collection of the standard model of perfluoroisopropyl hexanone or the near infrared spectrum of testing sample, transmission annex quartz glass tube being positioned near infrared gear carry out spectra collection.
Preferably, to the collection of the standard model of same perfluoroisopropyl hexanone or the near infrared spectrum of same testing sample at least in triplicate, and each continuous acquisition five spectrum, wherein, all spectrum of the standard model of perfluoroisopropyl hexanone change into a spectrum after equalization, and this spectrum represents the spectrum of the standard model of perfluoroisopropyl hexanone; All spectrum of testing sample change into a spectrum after equalization, and this spectrum represents the spectrum of sample to be tested.
The present invention, by the analysis modeling of Chemical Measurement, by setting detection limit, reaches and accurately identifies that whether unknown sample is the object of perfluoroisopropyl hexanone fire extinguishing agent.
Embodiment
Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The invention provides a kind of perfluoroisopropyl hexanone fire extinguishing agent recognition detection method, it is characterized in that, comprise the following steps:
Step one, mensuration testing sample are 4050cm to wave-number range
-1~ 5323cm
-1the absorption spectrum of near infrared light and the wave number of absorption peak;
Step 2, detection testing sample are 4065.2cm in wave number
-1(± 5cm
-1), 4670.8cm
-1(± 5cm
-1), 4790.3cm
-1(± 5cm
-1), 5280.1cm
-1(± 5cm
-1) whether place all have obvious absorption peak, if do not had, then judge to treat that test sample is as non-perfluorinated isopropyl hexanone fire extinguishing agent; If had, then enter next step and continue to detect;
Step 3, second order differentiate pre-service is carried out to the absorption spectrum of testing sample after, obtain the pre-processed spectrum of testing sample, and be 4061.3cm according to this spectrum in wave number section
-1~ 4636.1cm
-1corresponding derivative value sets up Euclidean distance model, similarity coefficient model or consistency check model;
Step 4, by the calculated value of described Euclidean distance model, similarity coefficient model or consistency check model with preset detection limit contrast, differentiate whether testing sample is perfluoroisopropyl hexanone fire extinguishing agent with this.
Concrete, owing to the spectrogram of testing sample and perfluoroisopropyl hexanone standard model will be contrasted, before step one, therefore also need the standard model measuring perfluoroisopropyl hexanone to be 4050cm to wave-number range
-1~ 5323cm
-1the absorption spectrum of near infrared light and the wave number of absorption peak; Certainly, the spectrogram measuring the standard model of perfluoroisopropyl hexanone can work as field recognition, also can be previously to have measured record.
The near infrared spectra collection of standard model is under constant temperature and humidity condition, by the special quartz glass tube of near infrared, gather the perfluoroisopropyl hexanone fire extinguishing agent that purity is greater than 99.0%, transmission annex quartz glass tube being placed near infrared gear carries out the collection of spectrum, at least three times are repeated for same standard model and carries out spectra collection, each continuous acquisition five spectrum, spectrum changes into a spectrum and represents standard model after equalization;
The near infrared spectra collection of testing sample is equally under constant temperature and humidity condition, testing sample is stored in quartz glass tube with liquid state, transmission annex quartz glass tube being placed near infrared gear carries out the collection of spectrum, at least in triplicate spectra collection is carried out for same testing sample, each continuous acquisition five spectrum, spectrum changes into a spectrum and represents unknown sample after equalization;
In addition, in order to obtain good spectrogram and spectroscopic data, described perfluoroisopropyl hexanone fire extinguishing agent recognition detection method also comprises carries out Pretreated spectra to original spectrum, and described Pretreated spectra comprises following treatments one or a combination set of: average centralization, standardization normalization, moving average is level and smooth, convolution is level and smooth, first order derivative, second derivative, convolution differentiate, standard normal variable conversion, multiplicative scatter correction, Fourier transform and wavelet transformation.
Preferably the original spectrum of testing sample is carried out to standard normal variable conversion and are level and smooth, the second order differentiate of five points difference width at 5 carrying out second order differentiate pre-service to the absorption spectrum of testing sample.
Below by three embodiments, the method is further described.
Embodiment one
Be 4049.8cm according to wave number section
-1~ 4998.6cm
-1and 5237.7cm
-1~ 5322.6cm
-1derivative value corresponding to pre-processed spectrum set up Euclidean distance model:
Wherein, i be [1 ,+∞) in natural number, x
ifor the derivative value that i-th wave number in the described wave number section in step 3 is corresponding, s
ioriginal spectrum for bromo-3,3, the 3-trifluoro propenes of 2-carries out the pretreated spectrum of the second order differentiate derivative value that i-th wave number is corresponding in described wave number section.
Definition x
ieuclidean distance value corresponding when=0 gets maximal value D
max, represent that two spectrum do not mate completely; Definition x
i=s
itime, corresponding Euclidean distance value gets minimum value D
min, represent that two spectrum mate completely; By D
maxand D
mingeometric ratio is linearly converted into the matching value between 0 ~ 100, if when the matching value calculated is not less than detection limit 95, then judges that testing sample is as perfluoroisopropyl hexanone fire extinguishing agent, otherwise is judged to be non-perfluorinated isopropyl hexanone fire extinguishing agent.
Seeing figures.1.and.2, by calculating, showing that this spectrum is at wave number section 4049.8cm
-1~ 4998.6cm
-1and 5237.7cm
-1~ 5322.6cm
-1d in scope
max=0.6223, and D
min=0;
By D
maxand D
mingeometric ratio is linearly converted into the matching value between 0 ~ 100, and namely 0.6223 and 0 (matching value) is corresponding, 0 (D
min) corresponding with 100 (matching values); Reduction formula: y=-160.694x+100 is calculated by above-mentioned two groups of data.
Adopting the method identical with standard model to carry out Pretreated spectra to 7 kinds of unknown samples, is D by the Euclidean distance discrimination model Euclidean distance value that can calculate between unknown sample and standard model set up
1, D
2, D
3, D
4, D
5, D
6, D
7, and by D according to D
maxand D
minby reduction formula y=-160.694x+100, be converted into matching value (wherein, negative value represents that testing sample goes out negative peak), be shown in Table 1, only have testing sample X
1matching value be greater than 95, therefore judge X
1for perfluoroisopropyl hexanone fire extinguishing agent (1230) (conveniently state, following to perfluoroisopropyl hexanone fire extinguishing agent all with 1230 fire extinguishing agents be called for short), all the other 6 kinds of sample equal non-perfluorinated isopropyl hexanone fire extinguishing agents.
Table 1 perfluoroisopropyl hexanone (1230) fire extinguishing agent Euclidean distance model prediction result
Derivative value after the pre-service of table 2 1230 fire extinguishing agent standard model original absorbance
Derivative value after the original absorbance value of table 3 unknown sample X3 and pre-service
Derivative value after the original absorbance of table 4 unknown sample X6 and pre-service
Wherein, the Data Source of table 2 and Fig. 1 and Fig. 2; Table 3 data from Fig. 3 and Fig. 4; Table 4 data from Fig. 5 and Fig. 6.
Embodiment two
Be 4049.8cm according to wave number section
-1~ 4998.6cm
-1and 5237.7cm
-1~ 5322.6cm
-1derivative value corresponding to pre-processed spectrum set up similarity coefficient model:
Wherein, R ∈ [-1,1], i ∈ [1 ,+∞) in natural number, x
ifor the derivative value that i-th beam location in the wave number section in step 3 is corresponding, s
ifor carrying out the pretreated spectrum of the second order differentiate derivative value that i-th wave number is corresponding in described wave number section to the original spectrum of perfluoroisopropyl hexanone,
for the mean value of the derivative value of testing sample in described wave number section, for testing sample in described wave number section
original spectrum for perfluoroisopropyl hexanone carries out the mean value of the derivative value of the pretreated spectrum of second order differentiate in described wave number section; Cov (x, s) and δ
xδ
svalue the closer to, represent testing sample more similar to 1230, namely when R value more close to 1 time, testing sample is more similar to 1230.
When R ∈ [-1,0], represent that the near infrared spectrum similarity of testing sample and perfluoroisopropyl hexanone is 0%, when when R ∈ (0,1] time, the near infrared spectrum similarity of expression testing sample and perfluoroisopropyl hexanone is R
0∈ (0% ~ 100%] between corresponding number percent, work as R
0when being not less than detection limit 95%, then judging that testing sample is as perfluoroisopropyl hexanone fire extinguishing agent, otherwise be judged to be non-perfluorinated isopropyl hexanone fire extinguishing agent.
Adopt the method identical with standard model to carry out Pretreated spectra to 7 kinds of unknown samples, related coefficient between unknown sample and standard model can be calculated by the related coefficient model set up.With reference to table 5, table 5 is 1203 fire extinguishing agent similarity coefficient model prediction results, is wherein only numbered X
1related coefficient more than 95%.
Table 5 perfluoroisopropyl hexanone (1230) fire extinguishing agent similarity coefficient model prediction result
Embodiment three
Choose 4049.8cm
-1~ 4998.6cm
-1and 5237.7cm
-1~ 5322.6cm
-1derivative value corresponding to pre-processed spectrum set up consistency check model:
Wherein, i ∈ [1 ,+∞) in natural number, x
ifor the derivative value that i-th beam location in the described wave number section in step 3 is corresponding, the derivative value mean value that i-th beam location of perfluoroisopropyl hexanone in described wave number section repeatedly measures is
standard deviation is σ; To each beam location derivative value mean value
add deduct the standard deviation (σ) of 3 times, then conforming limit value CI
limit=3, get 3 for detectability, work as CI
iwhen being less than detection limit 3, then judging that testing sample is as perfluoroisopropyl hexanone fire extinguishing agent, otherwise be judged to be non-perfluorinated isopropyl hexanone fire extinguishing agent.
Table 6 1230 fire extinguishing agent standard model is derivative value, mean value and standard deviation after pre-service repeatedly
Table 7 is for being 4049.8cm to 3303 fire extinguishing agent wave number sections
-1~ 4998.6cm
-1and 5237.7cm
-1~ 5322.6cm
-1corresponding derivative value carries out index of conformity CI
ithe result of calculation of value.
Table 7 perfluoroisopropyl hexanone (1230) fire extinguishing agent consistency model predicts the outcome
These are only the preferred embodiments of the present invention; not thereby the scope of the claims of the present invention is limited; every utilize instructions of the present invention and accompanying drawing content to do equivalent structure or equivalent flow process conversion; or be directly or indirectly used in other relevant technical fields, be all in like manner included in scope of patent protection of the present invention.