CN106770702B - Based on grey relevance analysis modified pitch aging research method - Google Patents

Based on grey relevance analysis modified pitch aging research method Download PDF

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CN106770702B
CN106770702B CN201611012428.3A CN201611012428A CN106770702B CN 106770702 B CN106770702 B CN 106770702B CN 201611012428 A CN201611012428 A CN 201611012428A CN 106770702 B CN106770702 B CN 106770702B
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grey
ratio
pitch
modified pitch
variation
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CN106770702A (en
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周燕
张凯
李美东
田华东
赵甜甜
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Tianjin Chengjian University
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography

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Abstract

The present invention discloses a kind of based on grey relevance analysis modified pitch aging research method, comprising the following steps: firstly, calculating the variation of molecular chain conformation before and after modified pitch aging;Then, the calculating of Grey Incidence parameter is carried out;Secondly, carrying out the grey relation entropy analysis that molecular weight distribution variation influences the variation of modified pitch macro property index;Again, influence sequence of the variation of molecular chain conformation to ageing properties is determined;Finally, the major influence factors of identified sign absorbed layer modified asphalt binders ageing-resistant performance, the quality for proof stress absorbed layer asphalt binder provide reference.The present invention is directed to by advanced analysis means, start with the relationship studied between the macro property of pitch and microstructure change from the microcosmic composition of pitch, inherently study the agine mechaism of pitch, guarantee that the use quality of road stress absorbing layer asphalt binder, the quality for proof stress absorbed layer asphalt binder provide reference.

Description

Based on grey relevance analysis modified pitch aging research method
Technical field
The invention belongs to technical field of road engineering, the method for being related to road stress absorbing layer modified pitch ageing properties is ground Study carefully more particularly to a kind of research method of the road stress absorbing layer modified pitch ageing properties based on grey relevance analysis.
Background technique
Gray relative analysis method, abbreviation grey relevance analysis are the effective means of poor information system analysis, are the Behavior-based control factors The microcosmic or macroscopical geometry of sequence is close, the influence degree between analysis factor, distinguishes that certainty factor is to master mainly with the secondary factor The effective ways estimated are contributed in behavior.The purpose is to INFORMATION OF INCOMPLETE and a small number of uncertain system are made the quantization between the factor, Sequence, and then analyzed from microcosmic angle.
Highway plays very important role in National Traffic System and national construction, since ageing of asphalt leads to highway Concrete Pavement Durability deficiency becomes the problem of road circle is paid close attention to always.Although China's road worker is also improving road Positive exploration and research are carried out in terms of the service performance and endurance quality in face, for pitch aging under effect of natural environment The existing more deep understanding of the change of physical property afterwards, however technology analysis of the ageing of asphalt on microcosmic level is also needed It is further perfect.
The constituent of pitch is extremely complex, and present technology is around asphalt component variation and pitch macro property mostly Relationship between variation, this has certain limitation for the research of ageing of asphalt mechanism.
Summary of the invention
The present invention is to overcome the deficiencies in the prior art described above, and proposes a kind of road stress absorbing layer based on grey relevance analysis The research method of modified pitch ageing properties.The microcosmic composition of material decides the property of material, therefore by advanced analysis Means are started with the relationship studied between the macro property of pitch and microstructure change, inherently from the microcosmic composition of pitch The agine mechaism for studying pitch finds out the various reasons for influencing ageing of asphalt, calculates pitch micro molecule using grey relevance analysis Amount, finds out Main Factors and the secondary factor by comparative analysis, judges that various molecular weight refer to six kinds of pitch macroscopical ageing properties Target influence degree, then carry out influence degree sequence, and then determine influence the maximum key factor of ageing of asphalt degree and The smallest factor provides important evidence to obtain the main indicator of ageing of asphalt mechanism for ageing of asphalt research.
The pitch macro property index that the present invention uses has: needle penetration, 135 DEG C of viscosity ratios, elasticity restore ratio, viscous toughness Than, 5 DEG C of Ductility ratios, mass ratioes, medium viscosity ratio, Ductility ratio are referring to 135 DEG C and 5 DEG C of Normalization rule;The pitch type used has: Seven kinds of SBR, SBS, SAM, QP, GC, TPS, STR representative stress absorbing layer modified pitch.
The technical solution adopted by the present invention to solve the technical problems: one kind being based on grey relevance analysis modified pitch ageing properties Research method, including following following steps:
A, the variation of molecular chain conformation before and after modified pitch aging is calculated;
B, the calculating of Grey Incidence parameter is carried out;
C, the grey relation entropy analysis that molecular weight distribution variation influences the variation of modified pitch macro property index is carried out;
D, influence sequence of the variation of molecular chain conformation to ageing properties is determined;
E, the major influence factors of identified sign absorbed layer modified asphalt binders ageing-resistant performance absorb for proof stress The quality of layer asphalt binder provides reference.
The method for calculating modified pitch aging front and back molecular chain conformation in the step a is gel permeation chromatography.
It includes gray relation grades, gray relational entropy and grey entropy relation grade that Grey Incidence parameter in the step b, which calculates,.
The modified pitch macro property index include penetration ratio, 135 DEG C of viscosity ratios, elasticity restore ratio, glutinous toughness ratio, 5 DEG C of Ductility ratios and mass ratio.
Compared with prior art the invention has the advantages that
1, start with from the microcosmic angle of pitch, thoroughly analyze molecular weight distribution variation to modified pitch ageing properties It influences, and selected parameter of the present invention is more, modified pitch ageing properties selecting index is comprehensive, and the conclusion obtained can accurately react Modified pitch ageing properties influence factor sequence.
2, for the present invention convenient for operation, influence factor is less, and condition limitation is few, is readily accomplished, and has practical application and promotion price Value.
Detailed description of the invention
Fig. 1 is the grey entropy relation grade that different parameters compare penetration ratio;
Fig. 2 is the grey entropy relation grade that different parameters compare 135 DEG C of viscosity ratios;
Fig. 3 is the grey entropy relation grade that different parameters compare that elasticity restores ratio;
Fig. 4 is the grey entropy relation grade that different parameters compare viscous toughness ratio;
Fig. 5 is the grey entropy relation grade that different parameters compare 5 DEG C of Ductility ratios;
Fig. 6 is the grey entropy relation grade that different parameters compare mass ratio.
Specific embodiment
Below by specific embodiments and the drawings, the present invention is further illustrated.The embodiment of the present invention is in order to more So that those skilled in the art is more fully understood the present invention well, any limitation is not made to the present invention.
One kind being based on grey relevance analysis modified pitch aging research method, including following following steps:
(a) seven kinds of modified pitch of the research of gel permeation chromatography isolation technics SBR, SBS, SAM, QP, GC, TPS, STR are utilized The distribution of ageing process middle-molecular-weihydroxyethyl and composition variation, and the variation of molecular chain conformation before and after modified pitch aging is counted It calculates;
(b) Grey Incidence relevant parameter (including gray relation grades, Hui Guan are carried out to seven kinds of modified pitch in above-mentioned steps Join entropy and grey entropy relation grade) calculating;
(c) grey relation entropy analysis that molecular weight distribution variation influences the variation of modified pitch macro property index is carried out;
(d) each aspect ratio before and after modified pitch aging is passed through into gray relational entropy meter from the ratio of different ageing properties indexs Grey entropy relation grade is calculated, influence sequence of the variation of molecular chain conformation to ageing properties is then determined according to grey entropy relation grade;
(e) major influence factors of stress absorbing layer modified asphalt binders ageing-resistant performance are determined, are proof stress The quality of absorbed layer asphalt binder provides reference.
It chooses seven kinds of modified pitch of SBR, SBS, SAM, QP, GC, TPS, STR to be studied, utilizes gel permeation chromatography Modifying agent and pitch phase aging forward backward averaging molecular weight is calculated, is used due to these three modified pitch of SBS, SAM, STR It is composite modifier, two modifying agent peaks (1 peak and 2 peaks) occurs.Modifying agent and pitch phase (being indicated with J) in each modified pitch The specific data of molecular weight are shown in Table 1~table 4 before and after aging.WhereinFor peak molecular weight,For number average molecular weight,For Weight average molecular mass, PD indicate dispersion degreeA indicates that peak area, A% indicate content of material.
Average molecular weight and distribution before 1 modifying agent aging of table
Average molecular weight and distribution after 2 modifying agent aging of table
Average molecular weight and distribution before 3 pitch phase aging of table
Average molecular weight and distribution after 4 pitch phase aging of table
Grey relevance analysis parameter calculates:
(1) gray relation grades
It is general to carry out that association factor collection primitive factor is converted into when grey correlation analysis.The definition of gray relative factor set Are as follows: set sequence X=(x1,x2,…,xr), F is the numerical value mapping ensemblen of X, and X is referred to as gray relative factor set as collecting χ.
{ first value, average value, maximization, minimum value, section value, positive divisor }
Gray relation grades calculation formula is X0∈ χ is comparison array, j=1,2 ... r.
Wherein, X0={ x0(i) Shu i=1,2 ..., r }, Xj={ xj(i) Shu i=1,2 ..., r }, then r (X0,Xj) meet ash pass Join four axioms: normative, even symmetry, globality and proximity, r are known as gray relation grades, claim r (X0(k),XjIt (k)) is gray relative Coefficient.Wherein, ξ is resolution ratio, generally takes 0.5.
(2) gray relational entropy
If χ is gray relative factor set, X0∈ χ is main ranks, Xj∈ χ, j=1,2 ... m are reference columns, { r (X0(k),Xj (k)) Shu k=1,2 ... n } then map Map:Rj→Pj
Referred to as grey relation coefficient distribution map, mapping value PhThe density value being referred to as distributed.Function:
For XjGray relational entropy.
(3) grey entropy relation grade
The grey entropy relation grade of sequence X j are as follows:
Wherein, HmThe maximum value of referred to as grey entropy, Hm(x)=lnn.N represents the different information column being made of n element most Big value.
Molecular weight distribution changes the grey relation entropy analysis influenced on modified pitch ageing properties:
(1) influence of each factor to penetration ratio
The ratio after modified asphalt modifier phase and pitch phase aging with parameter each before aging is calculated separately, is shown in Table 5, M is modifying agent phase part, and J is pitch phase part, and MPT indicates that peak molecular weight and ratio before aging after aging, MNT indicate that number is equal After molecular weight aging with the ratio before aging, MWT indicate weight average molecular weight aging after with the ratio before aging, PDT indicate dispersion It spends after aging with the ratio before aging, content and the ratio before aging after AT expression aging.
After 5 aging of table with aspect ratio each before aging
By after modified pitch aging not of the same race with penetration ratio before aging as principal act, modified asphalt modifier phase and drip Ratio after green phase aging with parameter each before aging is as factor set sequence, so that the original data series of grey relation entropy analysis are constituted, It is shown in Table 6.
The relationship of each aspect ratio of table 6 and Asphalt Penetration ratio
Since first value is to analyze from initial state the developing state of things, and equalization is from average sight Thought analyzes things development.The present invention carries out equalization transformation to original data series, i.e., removes sequence with the average value of sequence x All data in x, while all indexs are converted into positve term index, it generates ordered series of numbers and is shown in Table 7.
7 average value processing of table generates ordered series of numbers
It executes formula 1 and formula 2 calculates the grey relation coefficient of each influence index and penetration ratio, the results are shown in Table shown in 8:
8 grey relation coefficient of table
It executes formula 3 and grey entropy association density is calculated, the results are shown in Table shown in 9:
The grey entropy of table 9 is associated with density
The gray relational entropy that comparison array is calculated in formula 4 is executed, is shown in Table 10:
10 gray relational entropy of table
It executes formula 5 and grey entropy relation grade is calculated, the grey entropy of the ratio and needle penetration ratio of each parameter closes before and after aging Connection degree is shown in Fig. 1.
(2) influence of each factor to 135 DEG C of viscosity ratios
(1) gray relation grades, (2) gray relational entropy, (3) grey entropy relation grade in the calculating of grey relevance analysis parameter are repeated, and According to correlation test data it can be concluded that the variation of each molecular weight and its distribution is associated with the grey entropy of 135 DEG C of viscosity ratios before and after aging Degree, as shown in Fig. 2.
(3) each factor restores the influence of ratio to elasticity
(1) gray relation grades, (2) gray relational entropy, (3) grey entropy relation grade in the calculating of grey relevance analysis parameter are repeated, and According to correlation test data it can be concluded that the variation of each molecular weight and its distribution is associated with the grey entropy that elasticity restores ratio before and after aging Degree, as shown in Fig. 3.
(4) influence of each factor to viscous toughness ratio
(1) gray relation grades, (2) gray relational entropy, (3) grey entropy relation grade in the calculating of grey relevance analysis parameter are repeated, and According to correlation test data it can be concluded that gluing the grey entropy relation grade of toughness ratio before and after the variation of each molecular weight and its distribution and aging, As shown in Fig. 4.
(5) influence of each factor to 5 DEG C of Ductility ratios
(1) gray relation grades, (2) gray relational entropy, (3) grey entropy relation grade in the calculating of grey relevance analysis parameter are repeated, and According to correlation test data it can be concluded that the variation of each molecular weight and its distribution is associated with the grey entropy of 5 DEG C of Ductility ratios before and after aging Degree, as shown in Fig. 5.
(6) influence of each factor to mass ratio
(1) gray relation grades, (2) gray relational entropy, (3) grey entropy relation grade in the calculating of grey relevance analysis parameter are repeated, and According to correlation test data it can be concluded that before and after the variation of each molecular weight and its distribution and aging mass ratio grey entropy relation grade, i.e., For shown in Fig. 6.
Determine influence sequence of the variation of molecular chain conformation to ageing properties:
Fig. 1 shows influence size of each each aspect ratio of molecular chain conformation to penetration ratio before and after modified pitch aging Successively are as follows: pitch phase content ratio > pitch phase dispersion degree ratio > pitch phase peak molecular weight ratio > modifying agent weight average molecular weight ratio > Modifying agent number-average molecular weight ratio > pitch phase number-average molecular weight ratio > pitch phase weight average molecular weight ratio > modifying agent dispersion degree ratio > Modifying agent peak molecular weight ratio > modifier content ratio.
Fig. 2 shows influence of each each aspect ratio of molecular chain conformation to 135 DEG C of viscosity ratios before and after modified pitch aging Size is successively are as follows: pitch phase weight average molecular weight ratio > pitch phase number-average molecular weight ratio > pitch phase dispersion degree ratio > pitch phase content Divide equally than > pitch phase peak molecular weight ratio > modifying agent peak molecular weight ratio > modifying agent weight average molecular weight ratio > modifying agent number Son amount is than > modifying agent dispersion degree ratio > modifier content ratio.
Influence of each each aspect ratio of molecular chain conformation to elasticity recovery ratio is big before and after Fig. 3 shows modified pitch aging It is small successively are as follows: pitch phase dispersion degree ratio > pitch phase content ratio > pitch phase peak molecular weight ratio > pitch phase weight average molecular weight ratio > pitch phase number-average molecular weight ratio > modifying agent dispersion degree ratio > modifying agent weight average molecular weight ratio > modifying agent peak molecular weight ratio > modifying agent number-average molecular weight ratio > modifier content ratio.
Fig. 4 shows each each aspect ratio of molecular chain conformation in modified pitch aging front and back to the influence size of viscous toughness ratio Successively are as follows: pitch phase content ratio > pitch phase peak molecular weight ratio > pitch phase dispersion degree ratio > modifying agent dispersion degree ratio > pitch Phase number-average molecular weight ratio > modifying agent number-average molecular weight ratio > pitch phase weight average molecular weight ratio > modifying agent weight average molecular weight ratio > Modifying agent peak molecular weight ratio > modifier content ratio.
Influence of each each aspect ratio of molecular chain conformation to 5 DEG C of Ductility ratios is big before and after Fig. 5 shows modified pitch aging It is small successively are as follows: pitch phase content ratio > pitch phase weight average molecular weight ratio > pitch phase peak molecular weight ratio > modifying agent dispersion degree ratio > pitch phase dispersion degree ratio > modifying agent peak molecular weight ratio > pitch phase number-average molecular weight ratio > modifying agent weight average molecular weight ratio > modifier content ratio > modifying agent number-average molecular weight ratio.
Fig. 6 show before and after modified pitch aging influence size of each each aspect ratio of molecular chain conformation to mass ratio according to It is secondary are as follows: pitch phase content ratio > pitch phase peak molecular weight ratio > pitch phase dispersion degree ratio > pitch phase number-average molecular weight ratio > drip Green phase weight average molecular weight ratio > modifying agent weight average molecular weight ratio > modifying agent number-average molecular weight ratio > modifying agent dispersion degree ratio > changes Property agent peak molecular weight ratio > modifier content ratio.
The major influence factors of identified sign absorbed layer modified asphalt binders ageing-resistant performance:
By FIG. 1 to FIG. 6 and step (d) it can be concluded that influencing the maximum factor of modified pitch macro property is pitch phase The variation of molecular weight and dispersion degree, wherein the influence of pitch phase content ratio is maximum;And influence of the modifying agent to modified pitch aging It is smaller.And after modified pitch aging pitch phase variation compared with modifying agent influence of the variation to modified pitch aged properties more Greatly, so stress absorbing layer modified asphalt binders should pay attention to the selection of matrix pitch.
Specific implementation of the invention is described above, the present invention is not limited to the above specific embodiments, this Field technical staff can make various deformations or amendments within the scope of the claims, this has no effect on substance of the invention Content.
It should be understood that embodiment and example discussed herein simply to illustrate that, to those skilled in the art For, it can be improved or converted, and all these modifications and variations all should belong to the protection of appended claims of the present invention Range.

Claims (4)

1. being based on grey relevance analysis modified pitch aging research method, which comprises the following steps:
A, the variation of molecular chain conformation before and after modified pitch aging is calculated;
B, the calculating of Grey Incidence parameter is carried out;
C, the grey relation entropy analysis that molecular weight distribution variation influences the variation of modified pitch macro property index is carried out;
D, each aspect ratio before and after modified pitch aging is calculated from the ratio of different ageing properties indexs by gray relational entropy Grey entropy relation grade determines influence sequence of the variation of molecular chain conformation to ageing properties;
E, the major influence factors of identified sign absorbed layer modified asphalt binders ageing-resistant performance drip for proof stress absorbed layer The quality of green binder provides reference.
2. the method according to claim 1, wherein the calculating modified pitch aging front and back point in the step a Son amount and the method for distribution are gel permeation chromatography.
3. the method according to claim 1, wherein the Grey Incidence parameter calculating in the step b includes Gray relation grades, gray relational entropy and grey entropy relation grade.
4. according to claim 1 to method described in 3 any claims, which is characterized in that the modified pitch macro property Index includes penetration ratio, 135 DEG C of viscosity ratios, elasticity recovery ratio, glutinous toughness ratio, 5 DEG C of Ductility ratios and mass ratio.
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CN107798174A (en) * 2017-09-29 2018-03-13 长安大学 A kind of bituminous paving antiskid influence factor appraisal procedure based on grey relevance analysis
CN109540740A (en) * 2018-12-04 2019-03-29 江西蓝星星火有机硅有限公司 A kind of needle penetration fitting detection method of Molecular Weight of Silicone Rubber
CN112666105A (en) * 2020-12-04 2021-04-16 武汉科技大学 Asphalt high-temperature performance detection method based on gray entropy correlation
CN112415180B (en) * 2020-12-10 2021-09-10 广西交科集团有限公司 Method for selecting base asphalt for rubber asphalt based on ash correlation analysis
CN112630419B (en) * 2020-12-31 2022-02-11 同济大学 Method for judging asphalt aging degree in asphalt mixture

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