CN109900627B - Acid mist resistance evaluation method for solar energy absorption membrane for heat collector - Google Patents

Acid mist resistance evaluation method for solar energy absorption membrane for heat collector Download PDF

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CN109900627B
CN109900627B CN201711303398.6A CN201711303398A CN109900627B CN 109900627 B CN109900627 B CN 109900627B CN 201711303398 A CN201711303398 A CN 201711303398A CN 109900627 B CN109900627 B CN 109900627B
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acid mist
absorption film
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CN109900627A (en
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王吉宁
刘晓鹏
杜淼
米菁
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GRIMN Engineering Technology Research Institute Co Ltd
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Abstract

The invention discloses an acid mist resistance evaluation method of a solar energy absorption film for a heat collector. The method comprises the following steps: fixed H2SO4Measuring the change relation of the absorptivity alpha and emissivity epsilon of the absorption film under acid mist with different pH values along with the corrosion time T of the acid mist; taking acid mist with a certain specific pH value from the acid mist, and measuring the change relation of absorption films epsilon 1 and epsilon 0 along with the acid mist corrosion time T at different acid mist temperatures T, wherein T comprises T'; fitting different temperature and pH acid mist data to obtain expressions of the variation delta alpha and delta epsilon of the alpha and epsilon of the absorption film; substituting the delta alpha and the delta epsilon into the pc to be 0.5 delta epsilon-delta alpha to obtain an expression of the value of the absorption film pc, thereby achieving the purpose of predicting the acid mist resisting service life of the absorption film. In the above steps, the pH value of the acid mist is selected within the range of 4, 6.5]The selection range of acid mist temperature [293K, 333K]. The invention provides a specific method for evaluating the service life of the absorption film in the acid mist environment, and the acid mist resistance of the absorption film can be quantitatively evaluated.

Description

Acid mist resistance evaluation method for solar energy absorption membrane for heat collector
Technical Field
The invention relates to an acid mist resistance evaluation method of a solar energy absorption membrane for a heat collector, belonging to the technical field of weather resistance evaluation.
Background
The acid fog resistance of the solar energy absorption film for the heat collector is an important index for evaluating the weather resistance of the solar energy absorption film. The use environment of the heat collector in China is greatly different from that in Europe and America. In European and American countries, the absorption film of the heat collector mainly faces water vapor and trace SO in air2However, in China, the difference between the south and north regions and the environment makes the actual working conditions of the heat collector become very complicated, for example, the south China is rich in high humidity and salt fog, and the north China and the northwest China are rich in acid rain (acid fog), saline, alkaline and dust environments. At present, no quantitative test standard and method exist for evaluating the acid mist resistance of the absorption membrane for the heat collector. International Standard ISO 22975-3 Solar energy-Collector compositions and materials-Part 3: absorber surface along "gives the absorption film at 1ppm SO2Qualitative evaluation of service life under acid environment at 95% relative humidity and 20 ℃ test temperatureThe method can only qualitatively evaluate whether the absorption film has the service life of 25 years in an acid corrosion environment, but cannot give a quantitative relation between the performance of the absorption film and the pH value, the temperature T and the corrosion time T of the acid mist environment. The acid rain environment of China belongs to the sulfuric acid type, so that a life evaluation formula of the heat collector absorption film in the sulfuric acid type acid rain (acid mist) environment is given, and the method is of great importance in quantitatively reflecting the acid mist resistance of the absorption film and accurately predicting the life of the absorption film. In view of the above, it is necessary to develop a specific method for evaluating the life of the absorption film in an acid mist environment so as to quantitatively evaluate the acid mist resistance of the absorption film.
Disclosure of Invention
The invention aims to provide an acid mist resistance evaluation method of a solar energy absorption film for a heat collector, which quantificationally evaluates the acid mist tolerance of the absorption film by formulating specific steps of a service life evaluation method of the absorption film in an acid mist environment.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for evaluating acid mist resistance of a solar energy absorption film for a heat collector comprises the following steps:
(1) fixed H2SO4Measuring the change relation of the absorptivity alpha and emissivity epsilon of the absorption film under acid mist with different pH values along with the corrosion time T of the acid mist;
(2) taking a certain specific pH 'acid mist in the acid mist, and measuring the change relation between the absorptivity alpha and the emissivity epsilon of the absorption film at different acid mist temperatures T along with the corrosion time T of the acid mist, wherein T comprises T';
(3) and (4) fitting the acid mist data at different temperatures and different pH values to obtain the absorption rate variation delta alpha-alpha of the absorption film0And emissivity change delta epsilon-epsilon0The expression of (1);
(4) substituting the delta alpha and the delta epsilon into the pc to be 0.5 delta epsilon-delta alpha to obtain an expression of the value of the absorption film pc, thereby achieving the purpose of predicting the acid mist resisting service life of the absorption film.
Wherein, the alpha is0And ε0Initial absorption and emissivity representing the absorption film without acid mist corrosion; the pH value of the acid mist is not less than 4 and is within[4，6.5]Selecting within a range; the selected quantity of the acid mist temperature is more than or equal to 4, and the acid mist temperature is [293K, 333K%]Selecting within a range; the selected quantity of the acid mist corrosion time is more than or equal to 5; 3 parallel samples were made under each acid mist corrosion condition and the coating absorptivity and emissivity were calculated as average values.
The selection of the pH value, the temperature and the corrosion time point number of the acid mist aims at completely describing the change trend of the absorptivity and the emissivity; the selection range of the pH value [4, 6.5] of the acid mist and the selection range of the temperature [293K, 333K ] of the acid mist aim to be close to and cover the actual acid mist environment; the purpose of making 3 replicates per acid mist corrosion condition was to minimize experimental error introduced by individual differences in the test samples.
In the method for evaluating the acid fog resistance of the solar energy absorption film for the heat collector, fitting an expression of the absorption rate variation delta alpha of the absorption film comprises the following steps:
(1) adopt the formula
Figure BDA0001499770660000021
Expressing the change relation of the absorption rate alpha of the absorption film along with the acid mist environment;
(2) general formula
Figure BDA0001499770660000022
Simplified as y ═ a + bxnWhere y is α, x is t, and a is α0，
Figure BDA0001499770660000023
(3) Changing the absorption rate alpha of the absorption film under acid mist with different pH values and acid mist with different temperature T along with the corrosion time T of the acid mist according to the formula y ═ a + bxnFitting to obtain the power exponent n of each curve;
(4) averaging n obtained by fitting to obtain
Figure BDA0001499770660000024
Then, y is equal to a + bxnIs rewritten as
Figure BDA0001499770660000025
(5) The change relation of the absorption rate alpha of the absorption film under acid mist with specific pH and different temperatures T along with the corrosion time T of the acid mist is expressed according to the formula
Figure BDA0001499770660000026
Fitting to obtain the change relation of b along with the temperature T of the acid mist;
(6) general formula
Figure BDA0001499770660000027
Carrying out formula transformation, and taking logarithm at two sides of the equation to obtain the formula
Figure BDA0001499770660000028
(7) To pair
Figure BDA0001499770660000031
Linear fitting is carried out on the variation relation to obtain a linear slope k, and the slope k is
Figure BDA0001499770660000032
Since R is a constant, Q can be derivedeffThe exact value of (c);
(8) the change relation of the absorption rate alpha of the absorption film under the specific temperature T' and the acid mist with different pH values along with the acid mist corrosion time T is expressed according to the formula
Figure BDA0001499770660000033
Fitting to obtain the change relation of b along with the pH value of the acid mist;
(9) the relation between the pH value and the hydrogen ion concentration m is 10-pHFurther obtaining the change relation of b along with the concentration m of the acid mist hydrogen ions;
(10) to pair
Figure BDA0001499770660000034
Performing formula transformation to obtain
Figure BDA0001499770660000035
Will QeffSubstituting the exact value of (A) into the formula to obtain AThe change relation of A to m is changed along with the change relation of the hydrogen ion concentration m of the acid mist according to the formula A ═ pmqFitting to obtain a change relation of the concentration coefficient A along with the concentration m of the acid mist hydrogen ions;
(11) the relation between the pH value and the hydrogen ion concentration m is 10-pH，A＝pmqFurther rewritten as a ═ p (10)-qpH)
(12) Will be obtained
Figure BDA0001499770660000036
Qeff、A＝p(10-qpH) Substituted type
Figure BDA0001499770660000037
Obtaining the relation of the absorption rate alpha of the absorption film changing with the pH value, the temperature T and the corrosion time T of the acid mist
Figure BDA0001499770660000038
The absorption rate variable quantity delta alpha expression of the absorption film is
Figure BDA0001499770660000039
In the present invention, the absorption rate of the absorption film is related to the effective volume of the absorption film. Under the acid mist corrosion environment, the electrochemical diffusion reaction destroys the microstructure in the absorption film, and the consumption absorption layer forms a new phase, so that the volume of the effective absorption film is reduced, the absorption rate of the film is reduced, and the reduction of the absorption rate is related to the diffusion reaction rate. The Allen-nius equation is an empirical formula of chemical reaction rate, and on the basis of the analysis, the Allen-nius equation is used for constructing an expression of absorption rate in an acid mist corrosion environment of the absorption layer
Figure BDA00014997706600000310
Wherein A is a function of the pH (hydrogen ion concentration) of the acid mist, QeffThe effective activation energy representing the absorption rate change of the absorption film caused by acid mist corrosion is a constant, R is 8.31451J/(mol.K) is a mole gas constant, t represents the acid mist corrosion time, the power exponent n is a constant, and the effective activation energy Q iseffAnd the power index n is determined by the absorption film, therefore, in order to determine the relation of the absorption rate changing with the acid mist environment, the concentration coefficient equation A and the effective activation energy Q must be obtainedeffAnd a power exponent n.
Wherein, formula
Figure BDA0001499770660000041
Can be simplified to y ═ a + bxnWherein, y ═ α, x ═ t, and a ═ α0，
Figure BDA0001499770660000042
When the temperature of the acid mist is fixed, b is only related to the pH value (hydrogen ion concentration) of the acid mist.
The invention is based firstly on the principle that y is a + bxnFitting absorption rate data of the absorption film under acid mist with different pH values and different temperatures T, wherein each pH value and each temperature T are fitted with a power exponent n, and obtaining an average value
Figure BDA0001499770660000043
Figure BDA0001499770660000044
The error of the subsequent fitting can be reduced, and then the formula is rewritten into
Figure BDA0001499770660000045
The invention then follows
Figure BDA0001499770660000046
Fitting absorption rate data of the absorption film under acid mist with different temperatures T to obtain the change relation of b along with the temperature T of the acid mist, and then obtaining the formula
Figure BDA0001499770660000047
Taking logarithm at both sides simultaneously and carrying out formula transformation to obtain
Figure BDA0001499770660000048
It can be seen that
Figure BDA0001499770660000049
In a linearly changing relationship, pair
Figure BDA00014997706600000410
Performing a linear fit from the slope
Figure BDA00014997706600000411
The effective activation energy Q can be obtainedeff。
According to
Figure BDA00014997706600000412
Fitting the absorption rate data under acid mist with different pH values (hydrogen ion concentration) to obtain the corresponding change relationship between b and the pH value, wherein the functional relationship between m and the pH value is that m is 10-PHFurther, the corresponding relation between b and the hydrogen ion concentration m is obtained. In pair type
Figure BDA00014997706600000413
Performing formula transformation to obtain
Figure BDA00014997706600000414
Will QeffThe exact value of (A) is substituted into the formula to obtain a change relation curve of A to m, and generally speaking, the corrosion rate and the concentration of the acid mist hydrogen ions have an exponential change relation, so that the change relation curve of A to m is expressed by the formula of A ═ pmqFitting to obtain a relation of A changing with the acid mist concentration m, and changing m to 10-pHSubstituting to obtain the relation of A and pH value of acid mist, wherein A is p (10)-qpH)；
Will be obtained
Figure BDA00014997706600000415
Qeff、A＝p(10-qpH) Substituted type
Figure BDA00014997706600000416
Obtaining the relation of the change of the absorption rate alpha along with the pH value, the temperature T and the corrosion time T of the acid mist
Figure BDA00014997706600000417
The absorption rate variation delta alpha is expressed as
Figure BDA00014997706600000418
The method for evaluating the acid fog resistance of the solar absorbing film for the heat collector is characterized in that fitting of an expression of the emissivity change quantity delta epsilon of the absorbing film comprises the following steps:
(1) adopt the formula
Figure BDA00014997706600000419
Expressing the change relation of the emissivity epsilon of the absorption film along with the acid mist environment;
(2) general formula
Figure BDA0001499770660000051
Simplification to
Figure BDA0001499770660000052
Where y ═ epsilon, x ═ t, and a ═ epsilon0，
Figure BDA0001499770660000053
(3) The emissivity epsilon of the absorption film under acid mist with different pH values and acid mist with different temperatures T is changed along with the corrosion time T of the acid mist according to the formula
Figure BDA0001499770660000054
Fitting to obtain the power exponent n of each curve1And n2；
(4) N obtained by fitting1And n2Respectively take the average value
Figure BDA00014997706600000530
And
Figure BDA00014997706600000531
then will then
Figure BDA0001499770660000055
Is rewritten as
Figure BDA0001499770660000056
(5) The change relation of the emissivity epsilon of the absorption film under acid mist with specific pH and different temperatures T along with the corrosion time T of the acid mist is expressed according to the formula
Figure BDA0001499770660000057
Fitting to obtain the change relation between b and c along with the temperature T of the acid mist;
(6) general formula
Figure BDA0001499770660000058
And formula
Figure BDA0001499770660000059
Carrying out formula transformation, and taking logarithm at two sides of the equation to obtain the formula
Figure BDA00014997706600000510
And formula
Figure BDA00014997706600000511
(7) To pair
Figure BDA00014997706600000512
And
Figure BDA00014997706600000513
linear fitting is carried out on the variation relation to obtain a linear slope k1And k2Slope of
Figure BDA00014997706600000514
Since R is a constant, Q can be derived1And Q2The exact value of (c);
(8) the change relation of the emissivity epsilon of the absorbing film under the specific temperature T' and the acid mist with different pH values along with the acid mist corrosion time T is expressed according to the formula
Figure BDA00014997706600000515
Fitting to obtain the change relation of b and c along with the pH value of the acid mist;
(9) from pH valueThe relation m with the hydrogen ion concentration m is 10-pHFurther obtaining the change relation between b and c along with the concentration m of the acid mist hydrogen ions;
(10) to pair
Figure BDA00014997706600000516
And
Figure BDA00014997706600000517
performing formula transformation to obtain
Figure BDA00014997706600000518
And
Figure BDA00014997706600000519
will Q1And Q2Substituting the exact value of (A)1And A2Is expressed to obtain A1And A2According to the change relation of the acid mist concentration m, and A is1M change relationship and A2M is a variation relation expressed by the formula A ═ pmqFitting to obtain A1And A2Relation formula of change along with concentration m of acid mist
Figure BDA00014997706600000520
And
Figure BDA00014997706600000521
(11) the relation between the pH value and the hydrogen ion concentration m is 10-pH，
Figure BDA00014997706600000522
And
Figure BDA00014997706600000523
is further rewritten as
Figure BDA00014997706600000524
And
Figure BDA00014997706600000525
(12) will be obtained
Figure BDA00014997706600000526
Q1、Q2、
Figure BDA00014997706600000527
And
Figure BDA00014997706600000528
substituted type
Figure BDA00014997706600000529
Obtaining the change relation of the emissivity epsilon of the absorption film along with the pH value, the temperature T and the corrosion time T of the acid mist
Figure BDA0001499770660000061
The expression of the variation delta epsilon of the emissivity of the absorption film is
Figure BDA0001499770660000062
In the present invention, the emissivity of the absorbing film is related to the blackness index of the absorbing film surface, which is determined by two factors, i.e., the surface roughness and the surface material type. The emissivity expression is constructed similarly to absorptivity, and because emissivity is influenced by surface roughness and surface material types, the emissivity expression needs to contain two power exponential terms to obtain the following construction equation
Figure BDA0001499770660000063
Wherein the power term containing 1 represents the influence of surface roughness, the power term containing 2 represents the influence of new phase generation, A1、Q1And n1Respectively representing the concentration coefficient equation, activation energy and power exponent relating to the influence of surface roughness, A2、Q2And n2Respectively representing the concentration coefficient equation, activation energy and power exponent, Q, associated with the effect of new phase generation1、n1And Q2、n2All of which are constant and are determined by the absorption film, and therefore, in order to determine the change of the absorption rate with the acid mist environment, the concentration must be determinedDegree coefficient equation A1And A2Effective activation energy Q1And Q2And power exponent n1And n2. Determining method of each coefficient and determining method of corresponding coefficient of absorptivity, and finally obtaining emissivity variation delta epsilon expression
Figure BDA0001499770660000064
Substituting the obtained expressions of delta alpha and delta epsilon into pc which is 0.5 delta epsilon-delta alpha to obtain the expression relation of pc, namely
Figure BDA0001499770660000065
From the above equation, the service life T of the system absorption film under the acid mist corrosion can be determined by setting the pc value to 0.05 under the conditions of clear acid mist pH value and temperature T.
The invention has the advantages that:
the invention provides an acid mist resistance evaluation method of a solar energy absorption film for a heat collector. The acid mist tolerance of the absorption film can be quantitatively evaluated by formulating specific steps of the method for evaluating the service life of the absorption film in the acid mist environment.
Drawings
FIG. 1 is a flow chart of the method for evaluating the acid mist resistance of the solar absorbing film for the heat collector of the present invention.
FIG. 2 is a regression curve of data absorption at different pH values for example 1 of the present invention.
FIG. 3 is a graph showing the regression curves of absorbance for different temperature data in example 1 of the present invention.
FIG. 4 is a regression curve of data emissivity for different pH values of example 1 of the present invention.
FIG. 5 is an emissivity regression curve for different temperature data in example 1 of the present invention.
FIG. 6 is a regression curve of the pH value data pc of example 1 of the present invention.
FIG. 7 is a regression curve of pc values of different temperature data of example 1 of the present invention.
Detailed Description
The invention is further illustrated below with reference to the figures and examples, but the embodiments of the invention are not limited thereto.
As shown in fig. 1, the flow of the method for evaluating the acid mist resistance of the solar absorbing film for a heat collector of the present invention comprises:
(1) fixed H2SO4Measuring the change relation of the absorptivity alpha and emissivity epsilon of the absorption film under acid mist with different pH values along with the corrosion time T of the acid mist;
(2) taking a certain specific pH 'acid mist in the acid mist, and measuring the change relation between the absorptivity alpha and the emissivity epsilon of the absorption film at different acid mist temperatures T along with the corrosion time T of the acid mist, wherein T comprises T';
(3) and (4) fitting the acid mist data at different temperatures and different pH values to obtain the absorption rate variation delta alpha-alpha of the absorption film0And emissivity change delta epsilon-epsilon0The expression of (1);
(4) substituting the delta alpha and the delta epsilon into the pc to be 0.5 delta epsilon-delta alpha to obtain an expression of the value of the absorption film pc, thereby achieving the purpose of predicting the acid mist resisting service life of the absorption film.
The invention provides an acid mist resistance evaluation method of a solar energy absorption film for a heat collector. The acid mist tolerance of the absorption film can be quantitatively evaluated by formulating specific steps of the method for evaluating the service life of the absorption film in the acid mist environment.
Example 1
The absorbing film structure of the embodiment is SiO2(60nm)/Cr-CrNy(L-H) (80nm)/A1(0.30mm), the evaluation flow of acid mist weather resistance is as follows:
step 1: experiment of
(1) The fixed acid mist temperature is 308K, the pH values of the acid mist are 6.2, 5.3, 4.7 and 4, and the corrosion time of each pH acid mist is set to be 0h, 4h, 8h, 12h, 24h, 48h, 72h, 96h, 120h, 144h (according to the failure degree of the absorption film) and 168h (according to the failure degree of the absorption film);
(2) the pH value of the fixed acid mist is 5.3, the acid mist temperature is 298K, 308K, 318K and 328K, the acid mist corrosion time at each temperature is set to be 0h, 4h, 8h, 12h, 24h, 48h, 72h, 96h, 120h, 144h (according to the failure degree of the absorption film) and 168h (according to the failure degree of the absorption film);
(3) under each acid mist corrosion condition, three parallel samples are arranged, the absorption rate and the emissivity are the average values of the three samples, and the absorption rate and the emissivity of the absorption film are respectively 0.952 and 0.051 after the test.
Step 2: absorption rate variation delta alpha expression fitting of absorption film
(1) Adopt the formula
Figure BDA0001499770660000081
Expressing the change relation of the absorption rate alpha of the absorption film along with the acid mist environment;
(2) general formula
Figure BDA0001499770660000082
Simplified as y ═ a + bxnWhere y is α, x is t, and a is α0，
Figure BDA0001499770660000083
(3) Changing the absorption rate alpha of the absorption film under acid mist with different pH values and acid mist with different temperature T along with the corrosion time T of the acid mist according to the formula y ═ a + bxnFitting to obtain the power exponent n of each fitting curve;
(4) averaging n obtained by fitting to obtain
Figure BDA0001499770660000084
Then, y is equal to a + bxnIs rewritten as
Figure BDA0001499770660000085
(5) The change relation of the absorption rate alpha of the absorption film under different temperatures T acid mist with the pH value of 5.3 along with the corrosion time T of the acid mist is expressed according to the formula
Figure BDA0001499770660000086
Fitting to obtain the change relation of b along with the temperature T of the acid mist;
(6) general formula
Figure BDA0001499770660000087
Carrying out formula transformation, and taking logarithm at two sides of the equation to obtainGo out to formula
Figure BDA0001499770660000088
(7) To pair
Figure BDA0001499770660000089
Linear fitting is carried out on the variation relation to obtain a linear slope k and a slope
Figure BDA00014997706600000810
Since R is 8.31451J/(mol. K), Q is obtainedeff＝57.14366kJ/mol；
(8) The change relation of the absorption rate alpha of the absorption film under the acid mist with different pH values of 308K along with the corrosion time t of the acid mist is expressed according to the formula
Figure BDA00014997706600000811
Fitting to obtain the change relation of b along with the pH value of the acid mist;
(9) the relation between the pH value and the hydrogen ion concentration m is 10-PHFurther obtaining the change relation of b along with the concentration m of the acid mist hydrogen ions;
(10) to pair
Figure BDA00014997706600000812
Performing formula transformation to obtain
Figure BDA00014997706600000813
Will QeffSubstituting the exact value of the A into the formula to obtain the change relation of the A along with the concentration m of the hydrogen ions of the acid mist, and changing the relation of the A to the m according to the formula A as pmqFitting to obtain a concentration coefficient A which is 23.06785 m0.46723；
(11) The relation between the pH value and the hydrogen ion concentration m is 10-pH，A＝pmqFurther rewritten as a ═ p (0)-qpH)
(12) Will be obtained
Figure BDA00014997706600000921
、Qeff、A＝p(10-qpH) Substitute for Chinese traditional medicineGo into formula
Figure BDA0001499770660000091
Obtaining the relation of the absorption rate alpha of the absorption film changing with the pH value, the temperature T and the corrosion time T of the acid mist
Figure BDA0001499770660000092
The absorption rate variable quantity delta alpha expression of the absorption film is
Figure BDA0001499770660000093
The results of the regression fit of the absorption membrane absorption rates at different pH and different temperature T acid mist are shown in fig. 2 and 3.
And step 3: fitting of expression of variable quantity delta epsilon of emissivity of absorption film
(1) Adopt the formula
Figure BDA0001499770660000094
Expressing the change relation of the emissivity epsilon of the absorption film along with the acid mist environment;
(2) general formula
Figure BDA0001499770660000095
Simplification to
Figure BDA0001499770660000096
Where y ═ epsilon, x ═ t, and a ═ epsilon0，
Figure BDA0001499770660000097
(3) The emissivity epsilon of the absorption film under acid mist with different pH values and acid mist with different temperatures T is changed along with the corrosion time T of the acid mist according to the formula
Figure BDA0001499770660000098
Fitting to obtain n of each fitting curve1And n2；
(4) N obtained by fitting1And n2Respectively take the average value to obtain
Figure BDA0001499770660000099
And
Figure BDA00014997706600000910
then will be
Figure BDA00014997706600000911
Is rewritten as
Figure BDA00014997706600000912
(5) The change relation of the emissivity epsilon of the absorption film under different temperature T acid mist with the pH value of 5.3 and the corrosion time T of the acid mist is expressed according to the formula
Figure BDA00014997706600000913
Fitting to obtain the change relation between b and c along with the temperature T of the acid mist;
(6) general formula
Figure BDA00014997706600000914
And formula
Figure BDA00014997706600000915
Carrying out formula transformation, and taking logarithm at two sides of the equation to obtain the formula
Figure BDA00014997706600000916
And formula
Figure BDA00014997706600000917
(7) To pair
Figure BDA00014997706600000918
And
Figure BDA00014997706600000919
linear fitting is carried out on the variation relation to obtain a linear slope k1And k2Slope of
Figure BDA00014997706600000920
Q can be obtained by using R as 8.31451J/(mol. K)157.14887kJ/mol and Q2＝60.47422kJ/mol；
(8) The change relation of the emissivity epsilon of the absorbing film under the acid mist with different pH values of 308K along with the corrosion time t of the acid mist is expressed according to the formula
Figure BDA0001499770660000101
Fitting to obtain the change relation of b and c along with the pH value of the acid mist;
(9) the relation between the pH value and the hydrogen ion concentration m is 10-PHFurther obtaining the change relation between b and c along with the concentration m of the acid mist hydrogen ions;
(10) to pair
Figure BDA0001499770660000102
And
Figure BDA0001499770660000103
performing formula transformation to obtain
Figure BDA0001499770660000104
And
Figure BDA0001499770660000105
will Q1And Q2Substituting the exact value of (A)1And A2Is expressed to obtain A1And A2According to the change relation of the acid mist concentration m, and A is1M change relationship and A2M is a variation relation expressed by the formula A ═ pmqFitting to obtain A1And A2Relation A along with the change of acid mist concentration m1＝4.78423E8m0.32764And A2＝0.00325m0.45684；
(11) The relation between the pH value and the hydrogen ion concentration m is 10-pH，
Figure BDA0001499770660000106
And
Figure BDA0001499770660000107
is further rewritten as
Figure BDA0001499770660000108
And
Figure BDA0001499770660000109
(12) will be obtained
Figure BDA00014997706600001010
Q1、Q2、
Figure BDA00014997706600001011
And
Figure BDA00014997706600001012
substituted type
Figure BDA00014997706600001013
Obtaining the change relation of the emissivity epsilon of the absorption film along with the pH value, the temperature T and the corrosion time T of the acid mist
Figure BDA00014997706600001014
The expression of the variation delta epsilon of the emissivity of the absorption film is
Figure BDA00014997706600001015
The results of regression fitting of the emissivity of the absorbing film at different pH values and different temperatures under acid mist are shown in fig. 4 and 5.
And 4, step 4: lifetime evaluation formula and data regression
Substituting the obtained expressions of delta alpha and delta epsilon into pc which is 0.5 delta epsilon-delta alpha to obtain the expression relation of pc, namely
Figure BDA00014997706600001016
. The regression fitting results of the pc values of the absorption film at different pH values and different temperatures are shown in FIGS. 6 and 7, and the fitting results are ideal. From the above formula, the service life T of the system absorption film in the acid mist environment can be determined by setting the pc value to 0.05 under the conditions of clear acid mist pH value and temperature T.

Claims (3)

1. The method for evaluating the acid mist resistance of the solar energy absorption film for the heat collector is characterized by comprising the following steps of:
(1) fixed H2SO4Measuring the change relation of the absorptivity alpha and emissivity epsilon of the absorption film under acid mist with different pH values along with the corrosion time T of the acid mist;
(2) taking a certain specific pH 'acid mist in the acid mist, and measuring the change relation between the absorptivity alpha and the emissivity epsilon of the absorption film at different acid mist temperatures T along with the corrosion time T of the acid mist, wherein T comprises T';
(3) and (4) fitting the acid mist data at different temperatures and different pH values to obtain the absorption rate variation delta alpha-alpha of the absorption film0And emissivity change delta epsilon-epsilon0Wherein α is0And ε0Representing the initial absorptivity and emissivity of the absorbing film without acid mist corrosion, and alpha and epsilon representing the absorptivity and emissivity of the absorbing film after acid mist corrosion;
(4) substituting the delta alpha and the delta epsilon into the pc to be 0.5 delta epsilon-delta alpha to obtain an expression of the value pc of the absorption film, thereby achieving the purpose of predicting the acid mist resistant service life of the absorption film; wherein the content of the first and second substances,
the absorption rate variation quantity delta alpha expression fitting of the absorption film comprises the following steps:
(1) adopt the formula
Figure FDA0003017759960000011
Expressing the change relationship of the absorption rate alpha of the absorption film with the acid mist environment, A is a function of the pH value (hydrogen ion concentration) of the acid mist, and QeffThe effective activation energy representing the change of the absorptivity of the absorption film caused by acid mist corrosion, and R is a mole gas constant;
(2) general formula
Figure FDA0003017759960000012
Simplified as y ═ a + bxnWhere y is α, x is t, and a is α0，
Figure FDA0003017759960000013
(3) Changing the absorption rate alpha of the absorption film under acid mist with different pH values and acid mist with different temperature T along with the corrosion time T of the acid mist according to the formula y ═ a + bxnFitting to obtain the power exponent n of each curve;
(4) averaging n obtained by fitting to obtain
Figure FDA0003017759960000014
Then, y is equal to a + bxnIs rewritten as
Figure FDA0003017759960000015
(5) The change relation of the absorption rate alpha of the absorption film under acid mist with specific pH and different temperatures T along with the corrosion time T of the acid mist is expressed according to the formula
Figure FDA0003017759960000016
Fitting to obtain the change relation of b along with the temperature T of the acid mist;
(6) general formula
Figure FDA0003017759960000017
Carrying out formula transformation, and taking logarithm at two sides of the equation to obtain the formula
Figure FDA0003017759960000018
(7) To pair
Figure FDA0003017759960000021
Linear fitting is carried out on the variation relation to obtain a linear slope k, and the slope k is
Figure FDA0003017759960000022
Since R is a constant, Q can be derivedeffThe exact value of (c);
(8) the change relation of the absorption rate alpha of the absorption film under the specific temperature T' and the acid mist with different pH values along with the acid mist corrosion time T is expressed according to the formula
Figure FDA0003017759960000023
Fitting to obtain the change relation of b along with the pH value of the acid mist;
(9) from pH valueThe relation m with the hydrogen ion concentration m is 10-pHFurther obtaining the change relation of b along with the concentration m of the acid mist hydrogen ions;
(10) to pair
Figure FDA0003017759960000024
Performing formula transformation to obtain
Figure FDA0003017759960000025
Will QeffSubstituting the exact value of the A into the formula to obtain the change relation of the A along with the concentration m of the hydrogen ions of the acid mist, and changing the relation of the A to the m according to the formula A as pmqFitting to obtain a change relation of the concentration coefficient A along with the concentration m of the acid mist hydrogen ions;
(11) the relation between the pH value and the hydrogen ion concentration m is 10-pH，A＝pmqFurther rewritten as a ═ p (10)-qPH)；
(12) Will be obtained
Figure FDA0003017759960000026
Qeff、A＝p(10-qpH) Substituted type
Figure FDA0003017759960000027
Obtaining the relation of the absorption rate alpha of the absorption film changing with the pH value, the temperature T and the corrosion time T of the acid mist
Figure FDA0003017759960000028
The absorption rate variable quantity delta alpha expression of the absorption film is
Figure FDA0003017759960000029
The fitting of the expression of the variation delta epsilon of the emissivity of the absorption film comprises the following steps:
(1) adopt the formula
Figure FDA00030177599600000210
Expressing the change relation of the emissivity epsilon of the absorption film along with the acid mist environment, A1And A2Is a function of the pH (hydrogen ion concentration) of the acid mist, Q1Activation energy, Q, representing the change in emissivity caused by changes in surface roughness of the absorbing film during acid mist corrosion2Represents the activation energy of the absorption film in the acid mist corrosion process, wherein the new phase is generated to cause the change of emissivity;
(2) general formula
Figure FDA00030177599600000211
Simplification to
Figure FDA00030177599600000212
Where y ═ epsilon, x ═ t, and a ═ epsilon0，
Figure FDA00030177599600000213
(3) The emissivity epsilon of the absorption film under acid mist with different pH values and acid mist with different temperatures T is changed along with the corrosion time T of the acid mist according to the formula
Figure FDA00030177599600000214
Fitting to obtain the power exponent n of each curve1And n2；
(4) N obtained by fitting1And n2Respectively take the average value
Figure FDA00030177599600000215
And
Figure FDA00030177599600000216
then will be
Figure FDA00030177599600000217
Is rewritten as
Figure FDA0003017759960000031
(5) The change relation of the emissivity epsilon of the absorption film under acid mist with specific pH and different temperatures T along with the corrosion time T of the acid mist is expressed according to the formula
Figure FDA0003017759960000032
Fitting to obtain the change relation between b and c along with the temperature T of the acid mist;
(6) general formula
Figure FDA0003017759960000033
And formula
Figure FDA0003017759960000034
Carrying out formula transformation, and taking logarithm at two sides of the equation to obtain the formula
Figure FDA0003017759960000035
And formula
Figure FDA0003017759960000036
(7) To pair
Figure FDA0003017759960000037
And
Figure FDA0003017759960000038
linear fitting is carried out on the variation relation to obtain a linear slope k1And k2Slope of
Figure FDA0003017759960000039
Since R is a constant, Q can be derived1And Q2The exact value of (c);
(8) the change relation of the emissivity epsilon of the absorbing film under the specific temperature T' and the acid mist with different pH values along with the acid mist corrosion time T is expressed according to the formula
Figure FDA00030177599600000310
Fitting to obtain the change relation of b and c along with the pH value of the acid mist;
(9) the relation between the pH value and the concentration m of the hydrogen ions is that m is 10-pHFurther obtaining the change relation between b and c along with the concentration m of the acid mist hydrogen ions;
(10) to pair
Figure FDA00030177599600000311
And
Figure FDA00030177599600000312
performing formula transformation to obtain
Figure FDA00030177599600000313
And
Figure FDA00030177599600000314
will Q1And Q2Substituting the exact value of (A)1And A2Is expressed to obtain A1And A2According to the change relation of the acid mist concentration m, and A is1M change relationship and A2M is a variation relation expressed by the formula A ═ pmqFitting to obtain A1And A2Relation formula of change along with concentration m of acid mist
Figure FDA00030177599600000315
And
Figure FDA00030177599600000316
(11) the relation between the pH value and the concentration m of the hydrogen ions is that m is 10-pH，
Figure FDA00030177599600000317
And
Figure FDA00030177599600000318
is further rewritten as
Figure FDA00030177599600000319
And
Figure FDA00030177599600000320
(12) will be obtained
Figure FDA00030177599600000321
Q1、Q2、
Figure FDA00030177599600000322
And
Figure FDA00030177599600000323
substituted type
Figure FDA00030177599600000324
Obtaining the change relation of the emissivity epsilon of the absorption film along with the pH value, the temperature T and the corrosion time T of the acid mist
Figure FDA00030177599600000325
The expression of the variation delta epsilon of the emissivity of the absorption film is
Figure FDA00030177599600000326
Substituting the Δ α and Δ ∈ expressions obtained above into pc ═ 0.5 Δ ∈ - Δ α, yielding a pc expression relationship, i.e., a pc expression
Figure FDA00030177599600000327
From this equation, the service life T of the absorption film in an acid mist environment can be determined by setting the pc value to 0.05 under the conditions of clear acid mist pH value and temperature T.
2. The method of claim 1, wherein the acid mist resistance of the solar absorption membrane for a heat collector is selected to have a pH of 4 or more, the pH of the acid mist is selected to have a pH within a range of [4, 6.5], the temperature of the acid mist is selected to have a pH of 4 or more, the temperature of the acid mist is selected to have a pH within a range of [293K, 333K ], and the corrosion time of the acid mist is selected to have a pH of 5 or more.
3. The method for evaluating the acid mist resistance of a solar absorbing membrane for a heat collector as claimed in claim 1, wherein 3 parallel samples are taken per acid mist corrosion condition, and the coating absorptivity and emissivity are calculated as an average value.
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