CN106908170A - A kind of Raman frequency shift temp measuring method and system - Google Patents
A kind of Raman frequency shift temp measuring method and system Download PDFInfo
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- CN106908170A CN106908170A CN201710149999.XA CN201710149999A CN106908170A CN 106908170 A CN106908170 A CN 106908170A CN 201710149999 A CN201710149999 A CN 201710149999A CN 106908170 A CN106908170 A CN 106908170A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K11/00—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00
- G01K11/32—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using changes in transmittance, scattering or luminescence in optical fibres
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Abstract
The invention discloses a kind of Raman frequency shift temp measuring method and system, the present invention is, according to key relaxation theory, the Raman frequency shift thermometric algorithm of foundation, and to calculate accordingly result by configuring corresponding program.Compared with similar distributed fiber Raman temp measuring system, influence of the present invention without being bound by Raman scattering intensities size.The present invention not only can thermometric, moreover it is possible to the combination energy of effective predicting of substance, Debye temperature.Corresponding configuration software (APP cell phone platforms or PC application) of the invention compared with similar thermometric software, there is professional breakthrough.It not only has the similar temperature measuring application of computer, and more importantly：" with most commonly used cell phone system till now ", greatly facilitates and simplifies the operating process of thermometric personnel, while the Developing mainstream also with current era is closely related.
Description
Technical field：
The invention belongs to detection field, more particularly to a kind of Raman frequency shift temp measuring method and system.
Background technology：
Distributed fiberoptic sensor is strong because having the advantages that non-conductive, small volume, electromagnetism interference, therefore as in recent years
Come a kind of Novel temperature measuring sensor for developing rapidly.Its operation principle is a lot, there is liquid-core optical fibre OTDR (Rayleigh scattering), Raman
Scattering, Brillouin scattering, Guang Keer (kerr) effects and four-wave mixing etc..But what most distributed fiberoptic sensor was used
It is raman scattering intensity, that is, what is utilized is the ratio of the anti-Stokes light intensity Pas and Stokes light intensity Ps of spontaneous raman scattering generation
Value carrys out the temperature of measurement of species, and operation principle is complicated and is easily influenceed by raman scattering intensity.
In formula, C is temperature independent system constants, and λ as, λ s are respectively the ripples of anti-Stokes light and stokes light
Long, h is that Planck's constant, c are that the light velocity in vacuum, k are Boltzmann constant, and ν is wave number, and T is that fibre core temperature carry on the back and surveys object
Temperature.
The content of the invention：
It is an object of the invention to provide a kind of Raman frequency shift temp measuring method and system, the present invention is compared to other easily by temperature
The similar thermometry of the limitation of degree, patent of the present invention being capable of accurate measurement mass temperature interior in a big way；Patent of the present invention
The mass temperature being calculated should-(material temperature interior in the melting range of 1/3rd of material Debye temperature times and material
When degree exceedes melting temperature, its internal structure will change).By statistical analysis, the material Debye temperature being currently known is most
A height of diamond 2230K, minimum caesium 38K, average Debye temperature is in 300K or so.That is method of the present invention MDA temperature
Degree is about 13K.
To solve the above problems, the technical scheme is that：
A kind of Raman frequency shift temp measuring method, the temperature of testee is measured using Raman frequency shift value.
It is further to improve, obtain the Debye temperature of testee；Raman frequency shift according to testee is worth to be tested
The temperature of object, wherein Raman frequency shift are as follows with the relational expression of testee temperature：
Wherein,
Z represents the arest neighbors atomicity of testee material；zbThe ligancy of block materials is represented, ω (z, T) is coordinated for z
Raman frequency shift value of several materials under temperature T；ω(1,T0) it is material diatomic Raman frequency shift value；T represents testee
Temperature；T0Represent 0K；ω(zb,T0) by survey material be block size size when Raman frequency shift value；TmBy survey material it is molten
Point temperature；EbRepresent the bond energy of material wall scroll chemical bond；θDRepresent Debye temperature；η (T) represents the specific heat of wall scroll chemical bond, η (T)
=CV(T)/z, CVRepresent the specific heat of material；Ecoh=zEbRepresent atomic binding energy；X=θD/T；E represents natural constant；T>θD/3
When, singly-bound specific heat can be approximately equal to η=τ R/z, R ≈ 8.63*10^ (- 5) and represent ideal gas constant；τ represents dimension, τ=1,
2nd, 3 difference respective material dimensions are film dimensions size, shaft-like size and particle size；Block size size τ=
3。
If surveyed material is known substance, can consult that to obtain the diatomic Raman frequency shift value of material, block size big
Small Raman frequency shift value, the parameter input known to of atomic binding energy and singly-bound energy, by equation (1) and (3), measurement of species
Temperature value.
It is further to improve,
If surveyed material is unknown materials, using equation (2), and unknown materials are measured, confirmed respectively different
Parameter, comprises the following steps that：
Step one, the size that unknown materials are confirmed by measuring, determine the value of its dimension τ, τ=1,2,3 difference
Respective material dimension is film dimensions size, shaft-like size and particle size；And measure unknown materials block size
The Raman frequency shift value of size；
Step 2, the ligancy z that unknown materials are determined according to the size of material；If block materials, then z=12.Such as
Fruit is film dimensions size, shaft-like size and particle size for low-dimensional materials, then according to document " XX Yang, et
al.Raman spectroscopy determination of the Debye temperature and atomic
cohesive energy of CdS,CdSe,Bi2Se3,and Sb2Te3 nanostructures.Journal of
Applied Physics,2012.112(8):P.083508-083514. " carry out being calculated ligancy；
Step 3, according to document " XX Yang, et al.Raman spectroscopy determination of the
Debye temperature and atomic cohesive energy of CdS,CdSe,Bi2Se3,and Sb2Te3
nanostructures.Journal of Applied Physics,2012.112(8):P.083508-083514. " determine not
Know the diatomic Raman frequency shift value of material；
Step 4, the different Raman frequency shift values of measurement three or more than three and its corresponding temperature, the maximum Raman frequency shift of choosing
Two data outside value, and it is low by the big temperature of Raman frequency shift value, and the small temperature of Raman frequency shift value order high is drawn,
Obtain corresponding slope；By equation：
“((ω(zb, T) and-ω (1, T0)) * 0.5*3*8.63*10^ (- 5))/slope=Eb" unknown materials can be calculated
The bond energy of material wall scroll chemical bond；It is calculated atomic binding energy Ecoh=zEb；
Step 5, corresponding temperature value is obtained by equation (2) according to the Raman frequency shift value of unknown materials.
Further to improve, the Debye temperature of the testee is obtained by mensuration, concretely comprised the following steps：Step up
Or the temperature of testee is reduced, and the Raman frequency shift value of testee is measured, Raman frequency shift value becomes with the temperature of testee
The region changed and change is high-temperature region, and it is low-temperature space that Raman frequency shift value keeps constant region, the temperature of high-temperature region and low-temperature space
Separation is 1/3rd Debye temperature.
It is further to improve, the Raman spectrum of testee is measured, the Raman frequency shift value of testee is input to calculating
In machine, the temperature of testee is calculated.
It is further to improve, it is input into three or more than three the Raman frequency shift values and its corresponding temperature of different testees
Angle value, is calculated the current atomic binding energy of testee.T>θDWhen/3, η=3R/z, R ≈ 8.63x10^ (- 5) represent reason
Think gas constant；Calculate singly-bound energy algorithm：By being input into three data of different raman frequencies, two data of minimum are filtered out
Or two data are selected immediately after removing the data of maximum raman frequency, calculate curve of the two data in " frequency-temperature "
On slope, pass through.
“((ω(zb,T)-ω(1,T0)) * 0.5*3*8.63*10^ (- 5))/slope=Eb" list of the material can be calculated
Bond energy.
A kind of Raman frequency shift temp measuring system, including for the input block of input data, for the computing unit that calculates and
For the display unit of display output data；The computing formula that the computing unit is used is：
Further to improve, the Raman frequency shift temp measuring system is arranged on smart machine.
Further to improve, the smart machine is computer or mobile phone.
Advantages of the present invention is：
1st, compared to other easily by temperature limiting similar thermometry, patent of the present invention can accurate measurement in a big way
Interior mass temperature.
2nd, the mass temperature that patent of the present invention is calculated should be molten with material at 1/3rd of material Debye temperature times
In point temperature range-(when mass temperature exceedes melting temperature, its internal structure will change).By statistical analysis, at present
Known material Debye temperature is up to diamond 2230K, minimum caesium 38K, and average Debye temperature is in 300K or so.That is this hair
Bright method MDA temperature is about 13K.
Brief description of the drawings：
Fig. 1 is temperature of the diamond for measuring under different Raman frequency shifts；
Fig. 2 is by measuring the atomic binding energy that the testee temperature under three Raman frequency shifts is obtained, atomic binding energy
Ecoh=zEb。
Specific embodiment：
Embodiment 1
Formulation process of the invention is as follows：
1st, the relevance of bond parameter and size
Key relaxation theory (BOLS) core：Chemical bond bond distance (d) of low coordination atom (z) shortens Spontaneous Contraction, bond energy
Enhancing.It is mathematically represented as：
Subscript z and b have represented z arest neighbors Atomic coordinate number and block ligancy, b=12 respectively；CzBond distance shrinks system
Count, only the function of connective constant；M is key nature parameters；EcohRepresent atomic binding energy, EzRepresent that ligancy is the thing of z
The energy of matter wall scroll key, EbThe energy of wall scroll key when representing that material is block.
2nd, the relevance of bond parameter and Raman frequency shift
Pairing potential between atoms are launched with Taylor series, ignores Higher Order Perturbation, Raman frequency shift and bond parameter can be obtained
Proportional relation formula
ω (z) represents Raman spectrum frequency, and z and b has represented z arest neighbors Atomic coordinate number and block ligancy respectively.
dbRepresent block material bond distance, EzRepresent that ligancy is the energy of the material wall scroll key of z, μ is reduced mass, reduced mass μ=
m1m2/(m1+m2), non-phase transformation is then constant.
3rd, chemical bond and temperature dependence
When temperature and ligancy change, the bond distance d (T) of its material, the relation of bond energy E (T) follow following functional expression,
D (T) represents bond distance of the material at a temperature of T；dbBlock bond distance is represented, b represents block；α (t) represents thermal expansion system
Number；E (T) represents bond energy of the material at a temperature of T；EbRepresent the bond energy of material wall scroll chemical bond.η (t) represents wall scroll chemical bond
Specific heat；T represents the temperature of extraneous change；Unification is written as：EbRepresent the bond energy of material wall scroll chemical bond.
Approximate, the bond energy of thermal induction, it then follows following Debye specific heat relationship model formula according to debye,
θDRepresent Debye temperature；η (T) represents the specific heat of wall scroll chemical bond, η (T)=CV(T)/z, CVRepresent the ratio of material
Heat；Ecoh=zEbRepresent atomic binding energy；Z represents the arest neighbors atomicity of testee material；EbRepresent material wall scroll chemical bond
Bond energy.X represents θD/T；E represents natural constant.T>θDWhen/3, singly-bound specific heat η can be approximately equal to τ R=3R/z, and R represents preferable
Gas constant；τ represents dimension, and τ=1,2,3 difference respective material dimensions are film, shaft-like and particle；
With reference to equation (1)-(4), the relative changing value of Raman phonon vibration frequency and the relational expression of bond parameter,
Wherein,
Patent of the present invention is the Raman frequency shift thermometric algorithm of foundation according to key relaxation theory, and by configuring corresponding program
Calculate accordingly result.Compared with similar distributed fiber Raman temp measuring system, the present invention is without being bound by Raman scattering intensities
The influence of size.Patent of the present invention not only can thermometric, moreover it is possible to the combination energy of effective predicting of substance, Debye temperature.
The corresponding configuration software of patent (APP cell phone platforms or PC application) of the present invention compared with similar thermometric software,
There is professional breakthrough.It not only has the similar temperature measuring application of computer, and more importantly：" with the widest till now
On general cell phone system ", greatly facilitate and simplify the operating process of thermometric personnel, while also with the development master of current era
Stream is closely related.
It is as shown in Figure 1 the result that thermometric is carried out according to Raman frequency shift；Such as Fig. 2 is can be i.e. according to Raman frequency shift measurement singly-bound
The result of the bond energy of material wall scroll chemical bond, and the atomic binding energy of measured matter can be can obtain according to singly-bound, atom is combined
Can Ecoh=zEb。
Presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the invention, it is all in essence of the invention
Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.
Claims (9)
1. a kind of Raman frequency shift temp measuring method, it is characterised in that the temperature of testee is measured using Raman frequency shift value.
2. Raman frequency shift temp measuring method as claimed in claim 1, it is characterised in that obtain the Debye temperature of testee；Root
The temperature of testee, the wherein relational expression of Raman frequency shift and testee temperature are worth to according to the Raman frequency shift of testee such as
Under：
Wherein,
Z represents the arest neighbors atomicity of testee material；zbThe ligancy of block materials is represented, ω (z, T) is z ligancies
Raman frequency shift value of the material under temperature T；ω(1,T0) it is material diatomic Raman frequency shift value；T represents the temperature of testee；
T0Represent 0K；ω(zb,T0) by survey material be block size size when Raman frequency shift value；TmBy survey material fusing point temperature
Degree；EbRepresent the bond energy of material wall scroll chemical bond；θDRepresent Debye temperature；η (T) represents the specific heat of wall scroll chemical bond, η (T)=CV
(T)/z, CVRepresent the specific heat of material；Ecoh=zEbRepresent atomic binding energy；X=θD/T；E represents natural constant；T>θDWhen/3,
Singly-bound specific heat η=τ R/z, R ≈ 8.63*10^ (- 5) represents ideal gas constant；τ represents dimension, and τ=1,2,3 correspond to material respectively
Material dimension is film dimensions size, shaft-like size and particle size；
If surveyed material is known substance, can consult and obtain the diatomic Raman frequency shift value of material, block size size
Raman frequency shift value, atomic binding energy and singly-bound can be as known parameter inputs, by equation (1) and (3), the temperature of measurement of species
Value.
3. Raman frequency shift temp measuring method as claimed in claim 2, it is characterised in that
If surveyed material is unknown materials, using equation (2), and unknown materials are measured, different parameters are confirmed respectively,
Comprise the following steps that：
Step one, the size that unknown materials are confirmed by measuring, determine the value of its dimension τ, and τ=1,2,3 correspond to respectively
Material dimension is film dimensions size, shaft-like size and particle size；And measure unknown materials block size size
Raman frequency shift value；
Step 2, the ligancy z that unknown materials are determined according to the size of unknown materials；
Step 3, the diatomic Raman frequency shift value for determining unknown materials；
Step 4, the different Raman frequency shift values of measurement three or more than three and corresponding temperature, outside the maximum Raman frequency shift value of choosing
Two data, and low by the big temperature of Raman frequency shift value, the small temperature of Raman frequency shift value order high is drawn, and obtains right
The slope answered；By equation：
“((ω(zb, T) and-ω (1, T0)) * 0.5*3*8.63*10^ (- 5))/slope=Eb" material of unknown materials can be calculated
The bond energy of wall scroll chemical bond；It is calculated atomic binding energy Ecoh=zEb；
Step 5, corresponding temperature value is obtained by formula (2) according to the Raman frequency shift value of unknown materials.
4. the Raman frequency shift temp measuring method as described in claim 1-3 is any, it is characterised in that the debye temperature of the testee
Degree is obtained by mensuration, is concretely comprised the following steps：The temperature of testee is stepped up or reduced, and measures the Raman of testee
Frequency shift value, Raman frequency shift value is high-temperature region with the region that the temperature change of testee changes, and Raman frequency shift value keeps constant
Region be low-temperature space, the temperature trip point of high-temperature region and low-temperature space for 1/3rd Debye temperature.
5. Raman frequency shift temp measuring method as claimed in claim 2, it is characterised in that the Raman spectrum of measurement testee, will
The Raman frequency shift value of testee is input in computer, is calculated the temperature of testee.
6. Raman frequency shift temp measuring method as claimed in claim 2, it is characterised in that input three or more than three different quilts
The Raman frequency shift value and its corresponding temperature value of object are surveyed, the current atomic binding energy of testee is calculated.
7. a kind of Raman frequency shift temp measuring system, it is characterised in that including the input block for input data, based on calculating
Calculate unit and the display unit for display output data；The computing formula that the computing unit is used is：
8. Raman frequency shift temp measuring system as claimed in claim 7, it is characterised in that the Raman frequency shift temp measuring system is arranged on
On smart machine.
9. Raman frequency shift temp measuring system as claimed in claim 8, it is characterised in that the smart machine is computer or mobile phone.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110736499A (en) * | 2019-10-09 | 2020-01-31 | 清华大学 | Raman spectrum method for simultaneously measuring temperature and thermal stress of two-dimensional film material in situ |
| CN113916866A (en) * | 2021-10-19 | 2022-01-11 | 吉首大学 | Alloy material crystal structure detection method based on Raman spectrum analysis |
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| CN110736499A (en) * | 2019-10-09 | 2020-01-31 | 清华大学 | Raman spectrum method for simultaneously measuring temperature and thermal stress of two-dimensional film material in situ |
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| CN113916866A (en) * | 2021-10-19 | 2022-01-11 | 吉首大学 | Alloy material crystal structure detection method based on Raman spectrum analysis |
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