CN106908170B - 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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- CN106908170B CN106908170B CN201710149999.XA CN201710149999A CN106908170B CN 106908170 B CN106908170 B CN 106908170B CN 201710149999 A CN201710149999 A CN 201710149999A CN 106908170 B CN106908170 B CN 106908170B
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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
Abstract
The invention discloses a kind of Raman frequency shift temp measuring method and system, the invention patent is and to calculate accordingly result by configuring corresponding program according to key relaxation theory, the Raman frequency shift thermometric algorithm of foundation.Compared with similar distributed fiber Raman temp measuring system, influence of the present invention without being bound by Raman scattering intensities size.The invention patent not only can thermometric, moreover it is possible to the combination energy of effective predicting of substance, Debye temperature.The corresponding configuration software of the invention patent (APP cell phone platform or PC machine application) has professional breakthrough compared with similar thermometric software.The temperature measuring application that it not only has computer similar, and more importantly: " on most commonly used cell phone system till now " greatly facilitates and simplifies the operating process of thermometric personnel, while also closely related with the Developing mainstream of current era.
Description
Technical field:
The invention belongs to detection field more particularly to a kind of Raman frequency shift temp measuring method and systems.
Background technique:
Distributed fiberoptic sensor becomes in recent years because having many advantages, such as that non-conductive, small in size, electromagnetism interference is strong
Come a kind of Novel temperature measuring sensor rapidly developed.There are many its working principle, there is liquid-core optical fibre OTDR (Rayleigh scattering), Raman
Scattering, Brillouin scattering, Guang Keer (kerr) effect and four-wave mixing etc..But what most distributed fiberoptic sensor used
It is raman scattering intensity, that is, what is utilized is the ratio for the anti-Stokes light intensity Pas and Stokes light intensity Ps that spontaneous raman scattering generates
Value comes the temperature of measurement of species, working principle complexity and the influence vulnerable to raman scattering intensity.
In formula, C is temperature independent system constants, and λ as, λ s are the wave of anti-Stokes light and stokes light respectively
Long, h is Planck's constant, c is the light velocity in vacuum, k is Boltzmann constant, and ν is wave number, and T is that fibre core temperature carries on the back survey object
Temperature.
Summary of the invention:
The purpose of the present invention is to provide a kind of Raman frequency shift temp measuring method and systems, and the present invention is compared to other vulnerable to temperature
The similar thermometry of the limitation of degree, the invention patent being capable of mass temperatures in precise measurement larger range；The invention patent
The mass temperature being calculated should in the one third times of substance Debye temperature and the melting range of substance-(substance temperature
When degree is more than melting temperature, internal structure will change).By statistical analysis, the substance Debye temperature being currently known is most
A height of diamond 2230K, minimum caesium 38K, average Debye temperature is in 300K or so.Method minimum measurable temperature i.e. of the invention
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；It is tested according to the Raman frequency shift value of testee
The temperature of object, wherein Raman frequency shift and the relational expression of testee temperature are as follows:
Wherein,
The arest neighbors atomicity of z expression testee material；zbIndicate the ligancy of block materials, ω (z, T) is z coordination
Raman frequency shift value of several materials at temperature T；ω(1,T0) it is material diatomic Raman frequency shift value；T indicates testee
Temperature；T0Indicate 0K；ω(zb,T0) by survey substance be block size size when Raman frequency shift value；TmBy survey substance it is molten
Point temperature；EbIndicate the bond energy of substance single chemical bond；θDIndicate Debye temperature；η (T) indicates the specific heat of single chemical bond, η (T)
=CV(T)/z, CVIndicate the specific heat of material；Ecoh=zEbIndicate atomic binding energy；X=θD/T；E indicates natural constant；T>θD/3
When, singly-bound specific heat can be approximately equal to η=τ R/z, and R ≈ 8.63*10^ (- 5) indicates ideal gas constant；τ expression dimension, τ=1,
2,3 material dimension is respectively corresponded as film dimensions size, rod-shaped size and particle size；Block size size τ=
3。
If surveyed substance is known substance, diatomic Raman frequency shift value, the block size that can consult to obtain substance are big
Small Raman frequency shift value, atomic binding energy and singly-bound can be inputted as known parameter, by equation (1) and (3), measurement of species
Temperature value.
It is further to improve,
If surveyed substance is unknown materials, use equation (2), and unknown materials are measured, confirmation is different respectively
Parameter, the specific steps are as follows:
Step 1: determining the value of its dimension τ, τ=1,2,3 difference by the size of measurement confirmation unknown materials
Respective material dimension is film dimensions size, rod-shaped size and particle size；And measure unknown materials block size
The Raman frequency shift value of size；
Step 2: determining the ligancy z of unknown materials according to the size of material；If it is block materials, z=12.Such as
Fruit is low-dimensional materials, that is, film dimensions size, rod-shaped size and particle size, 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
2012.112 (8): p.083508-083514. " Applied Physics carries out that ligancy is calculated；
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
2012.112 (8): p.083508-083514. " nanostructures.Journal of Applied Physics is determined not
Know the diatomic Raman frequency shift value of substance；
Step 4: the different Raman frequency shift values of measurement three or three or more and its corresponding temperature, select maximum Raman frequency shift
Two data except value, and it is low by the big temperature of Raman frequency shift value, and the high sequence of the small temperature of Raman frequency shift value is drawn,
Obtain corresponding slope；Pass through equation:
“((ω(zb, T) and-ω (1, T0)) * 0.5*3*8.63*10^ (- 5))/slope=Eb" unknown materials can be calculated to obtain
The bond energy of substance single chemical bond；Atomic binding energy E is calculatedcoh=zEb；
Step 5: obtaining corresponding temperature value 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, specific steps are as follows: step up
Or the temperature of testee being reduced, and measure the Raman frequency shift value of testee, Raman frequency shift value becomes with the temperature of testee
The region changed and changed is high-temperature region, and the region that Raman frequency shift value remains unchanged is low-temperature space, the temperature of high-temperature region and low-temperature space
Separation is the Debye temperature of one third.
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, the Raman frequency shift value and its corresponding temperature of the different testee of input three or three or more
The current atomic binding energy of testee is calculated in angle value.T>θDWhen/3, η=3R/z, R ≈ 8.63x10^ (- 5) indicate reason
Think gas constant；It calculates singly-bound energy algorithm: by the data of input three different raman frequencies, filtering out the smallest two data
Or two data are selected immediately after removing the data of maximum raman frequency, the two data are calculated in the curve of " frequency-temperature "
On slope, pass through.
“((ω(zb,T)-ω(1,T0)) * 0.5*3*8.63*10^ (- 5))/slope=Eb" can calculate the substance list
Bond energy.
A kind of Raman frequency shift temp measuring system, including the input unit for input data, for calculating computing unit and
For showing the display unit of output data；The calculation formula that the computing unit uses are as follows:
Further to improve, the Raman frequency shift temp measuring system installation is on intelligent devices.
Further to improve, the smart machine is computer or mobile phone.
Advantages of the present invention are as follows:
1, compared to other similar thermometrys vulnerable to temperature limiting, the invention patent being capable of precise measurement larger range
Interior mass temperature.
2, the mass temperature that the invention patent is calculated should be in the one third times of substance Debye temperature and melting for substance
In point temperature range-(when mass temperature is more than melting temperature, internal structure will change).By statistical analysis, at present
Known substance 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 minimum measurable temperature is about 13K.
Detailed description of the invention:
Fig. 1 is the temperature of the diamond that measures under different Raman frequency shifts；
Fig. 2 is the atomic binding energy obtained by the testee temperature under three Raman frequency shifts of measurement, atomic binding energy
Ecoh=zEb。
Specific embodiment:
Embodiment 1
Formulation process of the invention is as follows:
1, the relevance of bond parameter and size
Key relaxation theory (BOLS) core: the chemical bond bond distance (d) of low coordination atom (z) shortens Spontaneous Contraction, bond energy
Enhancing.Its mathematical expression are as follows:
Subscript z and b have respectively represented z arest neighbors Atomic coordinate number and block ligancy, b=12；CzBond distance shrinks system
It counts, only the function of connective constant；M is key nature parameters；EcohIndicate atomic binding energy, EzIndicate that ligancy is the object of z
The energy of matter single key, EbIndicate the energy of single key when substance is block.
2, the relevance of bond parameter and Raman frequency shift
Pairing potential between atoms are unfolded with Taylor series, ignore Higher Order Perturbation item, Raman frequency shift and bond parameter can be obtained
Proportional relation formula
ω (z) indicates Raman spectrum frequency, and z and b have respectively represented z arest neighbors Atomic coordinate number and block ligancy.
dbIndicate block material bond distance, EzIndicating that ligancy is the energy of the substance single key of z, μ is reduced mass, reduced mass μ=
m1m2/(m1+m2), non-phase transformation is then constant.
3, chemical bond and temperature dependence
When temperature and ligancy change, the bond distance d (T) of material, the relationship of bond energy E (T) follow following functional expression,
D (T) indicates bond distance of substance at a temperature of T；dbIndicate that block bond distance, b indicate block；α (t) indicates thermal expansion system
Number；E (T) indicates bond energy of substance at a temperature of T；EbIndicate the bond energy of substance single chemical bond.η (t) indicates single chemical bond
Specific heat；T indicates the temperature of extraneous variation；It is uniformly written as: EbIndicate the bond energy of substance single chemical bond.
According to debye approximation, the bond energy of thermal induction, it then follows following Debye specific heat relationship model formula,
θDIndicate Debye temperature；η (T) indicates the specific heat of single chemical bond, η (T)=CV(T)/z, CVIndicate the ratio of material
Heat；Ecoh=zEbIndicate atomic binding energy；The arest neighbors atomicity of z expression testee material；EbIndicate substance single chemical bond
Bond energy.X indicates θD/T；E indicates natural constant.T>θDWhen/3, singly-bound specific heat η can be approximately equal to τ R=3R/z, and R indicates ideal
Gas constant；τ indicates dimension, and τ=1,2,3 respectively correspond material dimension as film, rod-shaped and particle；
In conjunction with equation (1)-(4), the relative changing value of Raman phonon vibration frequency and the relational expression of bond parameter,
Wherein,
The invention patent is according to key relaxation theory, the Raman frequency shift thermometric algorithm of foundation, 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.The invention patent not only can thermometric, moreover it is possible to the combination energy of effective predicting of substance, Debye temperature.
The corresponding configuration software of the invention patent (APP cell phone platform or PC machine application) compared with similar thermometric software,
There is professional breakthrough.The temperature measuring application that it not only has computer similar, 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
It flows closely related.
Result to carry out thermometric according to Raman frequency shift as shown in Figure 1；If Fig. 2 is to measure singly-bound according to Raman frequency shift can be
The bond energy of substance single chemical bond as a result, and the atomic binding energy of measured matter can be obtained according to singly-bound, atom combines
It can Ecoh=zEb。
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
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (7)
1. a kind of Raman frequency shift temp measuring method, which is characterized in that the temperature of testee is measured using Raman frequency shift value, including
Following steps: the Debye temperature of testee is obtained；The temperature of testee is obtained according to the Raman frequency shift value of testee,
Middle Raman frequency shift and the relational expression of testee temperature are as follows:
Wherein,
The arest neighbors atomicity of z expression testee material；zbIndicate the ligancy of block materials, ω (z, T) is z ligancy
Raman frequency shift value of the material at temperature T；ω(1,T0) it is material diatomic Raman frequency shift value；The temperature of T expression testee；
T0Indicate 0K；ω(zb,T0) by survey substance be block size size when Raman frequency shift value；TmBy survey substance fusing point temperature
Degree；EbIndicate the bond energy of substance single chemical bond；θDIndicate Debye temperature；η (T) indicates the specific heat of single chemical bond, η (T)=CV
(T)/z, CVIndicate the specific heat of material；Ecoh=zEbIndicate atomic binding energy；X=θD/T；E indicates natural constant；T>θDWhen/3,
Singly-bound specific heat η=τ R/z, R ≈ 8.63*10^ (- 5) indicates ideal gas constant；τ indicates dimension, and τ=1,2,3 respectively correspond material
Material dimension is film dimensions size, rod-shaped size and particle size；
Wherein, surveyed substance is unknown materials, using equation (2), and measures to unknown materials, confirms different ginsengs respectively
Number, the specific steps are as follows:
Step 1: determining the value of its dimension τ, τ=1,2,3 respectively correspond by the size of measurement confirmation unknown materials
Material dimension is film dimensions size, rod-shaped size and particle size；And measure unknown materials block size size
Raman frequency shift value；
Step 2: determining the ligancy z of unknown materials according to the size of unknown materials；
Step 3: determining the diatomic Raman frequency shift value of unknown materials；
Step 4: the different Raman frequency shift values of measurement three or three or more and corresponding temperature, are selected except maximum Raman frequency shift value
Two data, and low by the big temperature of Raman frequency shift value, the high sequence of the small temperature of Raman frequency shift value is drawn, and is obtained pair
The slope answered；Pass through equation:
“((ω(zb, T) and-ω (1, T0)) * 0.5*3*8.63*10^ (- 5))/slope=Eb" can calculate unknown materials substance
The bond energy of single chemical bond；Atomic binding energy E is calculatedcoh=zEb；
Step 5: obtaining corresponding temperature value by formula (2) according to the Raman frequency shift value of unknown materials.
2. Raman frequency shift temp measuring method as described in claim 1, which is characterized in that the Debye temperature of the testee passes through
Mensuration obtains, specific steps are as follows: steps up or reduces the temperature of testee, and measure the Raman frequency shift of testee
Value, the region that Raman frequency shift value changes with the temperature change of testee are high-temperature region, the area that Raman frequency shift value remains unchanged
Domain is low-temperature space, and the temperature trip point of high-temperature region and low-temperature space is the Debye temperature of one third.
3. Raman frequency shift temp measuring method as described in claim 1, which is characterized in that the Raman spectrum of testee is measured, it will
The Raman frequency shift value of testee is input in computer, and the temperature of testee is calculated.
4. Raman frequency shift temp measuring method as described in claim 1, which is characterized in that the different quilt of input three or three or more
The Raman frequency shift value of survey object and its corresponding temperature value, are calculated the current atomic binding energy of testee.
5. a kind of Raman frequency shift temp measuring system, which is characterized in that including the input unit for input data, based on calculating
Calculate unit and the display unit for showing output data；The calculation formula that the computing unit uses are as follows:
Wherein,
The arest neighbors atomicity of z expression testee material；zbIndicate the ligancy of block materials, ω (z, T) is z ligancy
Raman frequency shift value of the material at temperature T；ω(1,T0) it is material diatomic Raman frequency shift value；The temperature of T expression testee；
T0Indicate 0K；ω(zb,T0) by survey substance be block size size when Raman frequency shift value；TmBy survey substance fusing point temperature
Degree；EbIndicate the bond energy of substance single chemical bond；θDIndicate Debye temperature；η (T) indicates the specific heat of single chemical bond, η (T)=CV
(T)/z, CVIndicate the specific heat of material；Ecoh=zEbIndicate atomic binding energy；X=θD/T；E indicates natural constant；T>θDWhen/3,
Singly-bound specific heat η=τ R/z, R ≈ 8.63*10^ (- 5) indicates ideal gas constant；τ indicates dimension, and τ=1,2,3 respectively correspond material
Material dimension is film dimensions size, rod-shaped size and particle size；
Wherein, surveyed substance is unknown materials, using equation (2), and measures to unknown materials, confirms different ginsengs respectively
Number, the specific steps are as follows:
Step 1: determining the value of its dimension τ, τ=1,2,3 respectively correspond by the size of measurement confirmation unknown materials
Material dimension is film dimensions size, rod-shaped size and particle size；And measure unknown materials block size size
Raman frequency shift value；
Step 2: determining the ligancy z of unknown materials according to the size of unknown materials；
Step 3: determining the diatomic Raman frequency shift value of unknown materials；
Step 4: the different Raman frequency shift values of measurement three or three or more and corresponding temperature, are selected except maximum Raman frequency shift value
Two data, and low by the big temperature of Raman frequency shift value, the high sequence of the small temperature of Raman frequency shift value is drawn, and is obtained pair
The slope answered；Pass through equation:
“((ω(zb, T) and-ω (1, T0)) * 0.5*3*8.63*10^ (- 5))/slope=Eb" can calculate unknown materials substance
The bond energy of single chemical bond；Atomic binding energy E is calculatedcoh=zEb；
Step 5: obtaining corresponding temperature value by formula (2) according to the Raman frequency shift value of unknown materials.
6. Raman frequency shift temp measuring system as claimed in claim 5, which is characterized in that the Raman frequency shift temp measuring system is mounted on
On smart machine.
7. Raman frequency shift temp measuring system as claimed in claim 6, which is characterized in that the smart machine is computer or mobile phone.
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