CN106770702A - 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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CN106770702A
CN106770702A CN201611012428.3A CN201611012428A CN106770702A CN 106770702 A CN106770702 A CN 106770702A CN 201611012428 A CN201611012428 A CN 201611012428A CN 106770702 A CN106770702 A CN 106770702A
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pitch
grey
change
modified pitch
aging
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CN106770702B (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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  • Life Sciences & Earth Sciences (AREA)
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Abstract

The present invention discloses one kind based on grey relevance analysis modified pitch aging research method, comprises the following steps:First, the change of front and rear molecular chain conformation aging to modified pitch is calculated;Then, the calculating of Grey Incidence parameter is carried out;Secondly, grey relation entropy analysis of the molecular weight distribution change on the change influence of modified pitch macro property index are carried out;Again, influence of the change of molecular chain conformation to ageing properties is determined sequentially;Finally, the major influence factors of identified sign absorbed layer modified asphalt binders ageing-resistant performance, for the quality of proof stress absorbed layer asphalt binder provides reference.It is contemplated that by advanced analysis means, the relation started with from the microcosmic composition of pitch between the macro property and microstructure change of studying pitch, inherently study the agine mechaism of pitch, ensure the use quality of road stress absorbing layer asphalt binder, for the quality of proof stress absorbed layer asphalt binder provides reference.

Description

Based on grey relevance analysis modified pitch aging research method
Technical field
The invention belongs to road engineering technical field, it is related to the method for road stress absorbing layer modified pitch ageing properties to grind 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 technology
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 approached, the influence degree between analysis factor, distinguishes main with the secondary factor, and certainty factor is to master The effective ways that behavior contribution is estimated.The purpose is to INFORMATION OF INCOMPLETE and a small number of uncertain systems are made the quantization between the factor, Sequence, and then be analyzed from microcosmic angle.
Highway plays very important role in National Traffic System and national construction, because ageing of asphalt causes highway The problem paid close attention to always as road circle that Concrete Pavement Durability is not enough.Although China road work person is also improving road Performance and the endurance quality aspect in face carry out positive exploration and research, aging under effect of natural environment for pitch The change of physical property has more deep understanding afterwards, but the technical Analysis for ageing of asphalt on microcosmic level are also needed It is further perfect.
The constituent of pitch is extremely complex, and present technology is mostly around asphalt component change and pitch macro property Relation between change, this has certain limitation for the research of ageing of asphalt mechanism.
The content of the invention
The present invention proposes a kind of road stress absorbing layer based on grey relevance analysis to overcome above-mentioned deficiency of the prior art The research method of modified pitch ageing properties.The microcosmic composition of material decides the property of material, therefore by advanced analysis Means, the relation between the macro property and microstructure change of research pitch of starting with from the microcosmic composition of pitch, inherently The agine mechaism of pitch is studied, each side reason of influence ageing of asphalt is found out, pitch micro molecule is calculated using grey relevance analysis Amount, Main Factors and the secondary factor are obtained by comparative analysis, judge that various molecular weight refer to six kinds of macroscopical ageing properties of pitch Target influence degree, then carries out influence degree sequence, so determine the maximum key factor of influence ageing of asphalt degree and The minimum factor, so as to draw the leading indicator of ageing of asphalt mechanism, for ageing of asphalt research provides important evidence.
The pitch macro property index that the present invention is used has:Needle penetration, 135 DEG C of ratios of viscosities, elasticity recover ratio, viscous toughness Than, 5 DEG C of Ductility ratios, mass ratioes, wherein ratio of viscosities, Ductility ratio are with reference to 135 DEG C and 5 DEG C of Normalization rule;The pitch species for using has: Seven kinds of SBR, SBS, SAM, QP, GC, TPS, STR representative stress absorbing layer modified pitch.
The technical solution adopted for the present invention to solve the technical problems:One kind is based on grey relevance analysis modified pitch ageing properties Research method, including following following steps:
A, the change of front and rear molecular chain conformation aging to modified pitch are calculated;
B, the calculating for carrying out Grey Incidence parameter;
C, carry out molecular weight distribution change on modified pitch macro property index change influence grey relation entropy analysis;
D, determine influence of the change of molecular chain conformation to ageing properties sequentially;
The major influence factors of e, identified sign absorbed layer modified asphalt binders ageing-resistant performance, are that proof stress absorbs The quality of layer asphalt binder provides reference.
The method for calculating the aging front and rear molecular chain conformation of modified pitch in the step a is gel permeation chromatography.
Grey Incidence parameter in the step b is calculated and includes gray relation grades, gray relational entropy and grey entropy relation grade.
The modified pitch macro property index include penetration ratio, 135 DEG C of ratios of viscosities, elasticity recover ratio, glutinous Toughness Ratio, 5 DEG C of Ductility ratios and mass ratio.
Compared with prior art it is an advantage of the invention that:
1st, start with from the microcosmic angle of pitch, thoroughly analyze molecular weight distribution change to modified pitch ageing properties Influence, and selected parameter of the present invention is more, and comprehensively, the conclusion for drawing can react modified pitch ageing properties selecting index exactly Modified pitch ageing properties influence factor is sequentially.
2nd, the present invention is easy to operation, and influence factor is less, and condition limitation is few, is readily accomplished, with practical application and promotion price Value.
Brief description of the drawings
Fig. 1 is the grey entropy relation grade that different parameters compare penetration ratio;
Fig. 2 is that different parameters compare 135 DEG C of grey entropy relation grades of ratio of viscosities;
Fig. 3 is that different parameters compare the grey entropy relation grade that elasticity recovers ratio;
Fig. 4 is the grey entropy relation grade that different parameters compare viscous Toughness Ratio;
Fig. 5 is that different parameters compare 5 DEG C of grey entropy relation grades of Ductility ratio;
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.Embodiments of the invention are in order to more Those skilled in the art is more fully understood the present invention well, any limitation is not made to the present invention.
One kind is based on grey relevance analysis modified pitch aging research method, including following following steps:
A () utilizes gel permeation chromatography isolation technics research seven kinds of modified pitch of SBR, SBS, SAM, QP, GC, TPS, STR Ageing process middle-molecular-weihydroxyethyl is distributed and composition change, and the change of front and rear molecular chain conformation aging to modified pitch is counted Calculate;
(b) to above-mentioned steps in seven kinds of modified pitch carry out Grey Incidence relevant parameter (including gray relation grades, Hui Guan Connection entropy and grey entropy relation grade) calculating;
C () carries out grey relation entropy analysis of the molecular weight distribution change on the change influence of modified pitch macro property index;
D the aging front and rear each aspect ratio of modified pitch is passed through gray relational entropy meter by () from the ratio of different ageing properties indexs Grey entropy relation grade is calculated, influence of the change of molecular chain conformation to ageing properties is then determined according to grey entropy relation grade sequentially;
E () determines the major influence factors of stress absorbing layer modified asphalt binders ageing-resistant performance, be proof stress The quality of absorbed layer asphalt binder provides reference.
Choose seven kinds of modified pitch of SBR, SBS, SAM, QP, GC, TPS, STR to be studied, using gel permeation chromatography Modifying agent forward backward averaging molecular weight mutually aging with pitch is calculated, due to SBS, SAM, STR these three modified pitch use It is composite modifier, occurs in that two modifying agent peaks (1 peak and 2 peaks).Modifying agent and pitch phase (being represented with J) in each modified pitch The specific data of molecular weight are shown in Table 1~table 4 before and after aging.WhereinIt is peak molecular weight,It is several equal molecular masses,For Weight average molecular mass, PD represents decentralizationA represents peak area, and A% represents content of material.
The aging preceding mean molecule quantity of the modifying agent of table 1 and distribution
The aging rear mean molecule quantity of the modifying agent of table 2 and distribution
The mutually aging preceding mean molecule quantity of the pitch of table 3 and distribution
The mutually aging rear mean molecule quantity of the pitch of table 4 and distribution
Grey relevance analysis parameter is calculated:
(1) gray relation grades
Primitive factor will be converted into association factor collection when typically carrying out grey correlation analysis.Gray relative factor set is defined For:If sequence X=(x1,x2,…,xr), F is the numerical value mapping ensemblen of X, and X is called gray relative factor set as collecting χ.
{ just value, average value, maximization, minimum value, interval value, positive divisor }
Gray relation grades computing formula is X0∈ χ are 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:Normalization, even symmetry, globality and proximity, r are referred to as gray relation grades, claim r (X0(k),Xj(k)) it is gray relative Coefficient.Wherein, ξ is resolution ratio, typically takes 0.5.
(2) gray relational entropy
If χ is gray relative factor set, X0∈ χ are 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:
It is XjGray relational entropy.
(3) grey entropy relation grade
The grey entropy relation grade of sequence X j is:
Wherein, HmThe maximum of referred to as grey entropy, Hm(x)=lnn.N represents the different information row being made up of n element most Big value.
Grey relation entropy analysis of the molecular weight distribution change on the influence of modified pitch ageing properties:
(1) influence of each factor to penetration ratio
Ratio after calculating modified asphalt modifier phase and pitch are mutually aging respectively with aging preceding each parameter, is shown in Table 5, M is modifying agent phase part, and J is pitch phase part, and MPT represents aging rear peak molecular weight and aging preceding ratio, and MNT represents that number is equal With aging preceding ratio after molecular weight is aging, MWT represents that weight average molecular weight represents dispersion after aging with aging preceding ratio, PDT Represent aging rear content with aging preceding ratio with aging preceding ratio, AT after degree is aging.
With aging preceding each aspect ratio after table 5 is aging
By modified pitch not of the same race it is aging after with aging preceding penetration ratio as principal act, modified asphalt modifier phase and drip It is blue or green it is mutually aging after with the ratio of aging preceding each parameter as factor set sequence, so as to constitute the original data series of grey relation entropy analysis, It is shown in Table 6.
Each aspect ratio of table 6 and Asphalt Penetration than relation
Because first value is that, from initial state, the developing state to things is analyzed, and equalization is from average sight Thought is analyzed to things development.The present invention carries out equalization conversion to original data series, i.e., remove sequence with the average value of sequence x All of data in x, while all indexs are converted into positve term index, generation ordered series of numbers is shown in Table 7.
The average value processing of table 7 produces ordered series of numbers
Perform 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:
The grey relation coefficient of table 8
Perform formula 3 and calculate ash discharge entropy association density, the results are shown in Table shown in 9:
The grey entropy association density of table 9
The gray relational entropy that formula 4 calculates comparison array is performed, is shown in Table 10:
The gray relational entropy of table 10
Perform formula 5 and calculate grey entropy relation grade, ratio and the grey entropy of needle penetration ratio of aging front and rear each parameter are closed Connection degree is shown in Fig. 1.
(2) each factor is to 135 DEG C of influences of ratio of viscosities
(1) gray relation grades, (2) gray relational entropy, (3) grey entropy relation grade during grey relevance analysis parameter is calculated are repeated, and Can show that each molecular weight and its change of distribution are associated with the grey entropy of aging front and rear 135 DEG C of ratios of viscosities according to correlation test data Degree, as shown in Fig. 2.
(3) each factor recovers the influence of ratio to elasticity
(1) gray relation grades, (2) gray relational entropy, (3) grey entropy relation grade during grey relevance analysis parameter is calculated are repeated, and Can show that each molecular weight and its change of distribution are associated with the grey entropy of aging front and rear elasticity recovery ratio according to correlation test data 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 during grey relevance analysis parameter is calculated are repeated, and The change of each molecular weight and its distribution and the grey entropy relation grade of aging front and rear viscous Toughness Ratio can be drawn according to correlation test data, As shown in Fig. 4.
(5) each factor is to 5 DEG C of influences of Ductility ratio
(1) gray relation grades, (2) gray relational entropy, (3) grey entropy relation grade during grey relevance analysis parameter is calculated are repeated, and Can show that each molecular weight and its change of distribution are associated with the grey entropy of aging front and rear 5 DEG C of Ductility ratios according to correlation test data 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 during grey relevance analysis parameter is calculated are repeated, and The change of each molecular weight and its distribution and the grey entropy relation grade of aging front and rear mass ratio can be drawn according to correlation test data, i.e., Shown in Fig. 6.
Determine influence of the change of molecular chain conformation to ageing properties sequentially:
Fig. 1 shows aging front and rear influence size of each each aspect ratio of molecular chain conformation to penetration ratio of modified pitch It is followed successively by:Pitch phase content compares > than > pitch phase peak molecular weights than > pitch phase decentralization than > modifying agent weight average molecular weight Modifying agent number-average molecular weight compares > than > pitch phase weight average molecular weight than > pitch phase number-average molecular weights than > modifying agent decentralization Modifying agent peak molecular weight is than > modifier contents ratio.
Fig. 2 shows the aging front and rear each each aspect ratio of molecular chain conformation of modified pitch to 135 DEG C of influences of ratio of viscosities Size is followed successively by:Pitch phase weight average molecular weight is than > pitch phase number-average molecular weights than > pitch phase decentralization than > pitch phase contents Divide equally than > modifying agent numbers than > modifying agent weight average molecular weight than > modifying agent peak molecular weight than > pitch phase peak molecular weights Son amount is than > modifying agent decentralization than > modifier contents ratio.
Fig. 3 shows that influence of the aging front and rear each each aspect ratio of molecular chain conformation of modified pitch to elasticity recovery ratio is big It is small to be followed successively by:Pitch phase decentralization is than > pitch phase contents than > pitch phase peak molecular weights than > pitch phase weight average molecular weight ratios > pitch phase number-average molecular weights are than > modifying agent decentralization than > modifying agent weight average molecular weight than > modifying agent peak molecular weight ratio > modifying agent number-average molecular weight is than > modifier contents ratio.
Fig. 4 shows the aging front and rear each each aspect ratio of molecular chain conformation of modified pitch to gluing the influence size of Toughness Ratio It is followed successively by:Pitch phase content than > pitch phase peak molecular weights than > pitch phase decentralization than > modifying agent decentralization than > pitch Phase number-average molecular weight compares > than > pitch phase weight average molecular weight than > modifying agent number-average molecular weight than > modifying agent weight average molecular weight Modifying agent peak molecular weight is than > modifier contents ratio.
Fig. 5 shows that aging front and rear influence of each each aspect ratio of molecular chain conformation to 5 DEG C of Ductility ratios of modified pitch is big It is small to be followed successively by:Pitch phase content is than > pitch phase weight average molecular weight than > pitch phase peak molecular weights than > modifying agent decentralization ratio > pitch phase decentralization is than > modifying agent peak molecular weight than > pitch phase number-average molecular weights than > modifying agent weight average molecular weight ratio > modifier contents are than > modifying agent number-average molecular weight ratio.
Fig. 6 show modified pitch it is aging before and after influence size of each each aspect ratio of molecular chain conformation to mass ratio according to It is secondary to be:Pitch phase content is dripped than > pitch phase number-average molecular weights than > pitch phase decentralization than > pitch phase peak molecular weights than > Blue or green phase weight average molecular weight changes than > modifying agent decentralization than > modifying agent number-average molecular weight than > modifying agent weight average molecular weight than > Property agent peak molecular weight is than > modifier contents ratio.
The major influence factors of identified sign absorbed layer modified asphalt binders ageing-resistant performance:
Can show that the maximum factor of influence modified pitch macro property is pitch phase by Fig. 1~Fig. 6 and step (d) The change of molecular weight and decentralization, wherein pitch phase content than influence it is maximum;And the modifying agent influence aging to modified pitch It is smaller.And influence of the change of the change compared with modifying agent of the aging rear pitch phase of modified pitch to modified pitch aged properties is 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 Art personnel can within the scope of the claims make various deformations or amendments, and this has no effect on substance of the invention Content.
It should be appreciated that embodiment discussed herein and example simply to illustrate that, to those skilled in the art For, can be improved or be converted, and all these modifications and variations should all belong to the protection of appended claims of the present invention Scope.

Claims (4)

1. grey relevance analysis modified pitch aging research method is based on, it is characterised in that comprised the following steps:
A, the change of front and rear molecular chain conformation aging to modified pitch are calculated;
B, the calculating for carrying out Grey Incidence parameter;
C, carry out molecular weight distribution change on modified pitch macro property index change influence grey relation entropy analysis;
D, determine influence of the change of molecular chain conformation to ageing properties sequentially;
The major influence factors of e, identified sign absorbed layer modified asphalt binders ageing-resistant performance, are the drip of proof stress absorbed layer The quality of blue or green binder provides reference.
2. method according to claim 1, it is characterised in that before and after calculating modified pitch in the step a is aging point Son amount and the method for distribution are gel permeation chromatography.
3. method according to claim 1, it is characterised in that the Grey Incidence parameter in the step b is calculated and included Gray relation grades, gray relational entropy and grey entropy relation grade.
4. the method according to claims 1 to 3 any claim, it is characterised in that the modified pitch macro property Index includes that penetration ratio, 135 DEG C of ratios of viscosities, elasticity recover 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
CN112415180A (en) * 2020-12-10 2021-02-26 广西交科集团有限公司 Method for selecting base asphalt for rubber asphalt based on ash correlation analysis
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
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CN112630419A (en) * 2020-12-31 2021-04-09 同济大学 Method for judging asphalt aging degree in asphalt mixture
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