CN103115942A - Heat conductivity coefficient multi-scale prediction method for hardened portland cement paste - Google Patents

Heat conductivity coefficient multi-scale prediction method for hardened portland cement paste Download PDF

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CN103115942A
CN103115942A CN2013100309241A CN201310030924A CN103115942A CN 103115942 A CN103115942 A CN 103115942A CN 2013100309241 A CN2013100309241 A CN 2013100309241A CN 201310030924 A CN201310030924 A CN 201310030924A CN 103115942 A CN103115942 A CN 103115942A
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heat conductivity
coefficient
homogenising
phase
yardstick
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赵海涛
吴胜兴
魏珍中
张风臣
曹秀丽
陈育志
骆勇军
王溢
唐易民
朱晓琳
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Hohai University HHU
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Abstract

The invention discloses a heat conductivity coefficient multi-scale prediction method for hardened portland cement paste. The method disclosed by the invention comprises the following steps of: performing multi-phase and multi-scale division according to the microstructure and the composition of the hardened portland cement paste, enabling each scale to contain a typical phase, then calculating the volume percentages of the different phases, and further calculating a heat conductivity coefficient of the hardened portland cement paste through a generalized self-consistent method according to the volume percentage, the heat conductivity coefficient and other parameters of each phase on each scale. According to the method disclosed by the invention, the influence of the microstructure and the performances of composition materials of the hardened portland cement paste on the macroscopic heat conductivity coefficient of the cement paste is considered, the considered influence factors are comprehensive and reasonable, the form is simple and the use is convenient. A prediction model constructed according to the method can predict the heat conductivity coefficients of the hardened portland cement paste with different water-cement ratios and different types of cement more accurately.

Description

The sclerosis Portland cement is starched coefficient of heat conductivity multi-scale prediction method only
Technical field
The present invention relates to a kind of sclerosis Portland cement and only starch coefficient of heat conductivity multi-scale prediction method, belong to the cement-based material technical field.
Background technology
Coefficient of heat conductivity is one of basic thermal property of hardening cement base material, is also one of most important parameter of carrying out structural design, and whether value rationally is directly connected to structural internal force, the temperature reinforcement quantity of reinforcement calculates.Both at home and abroad the researcher has carried out a large amount of experimental studies to the cement-based material macro property, attempts to illustrate the quantitative relationship of cement-based material match ratio, cement consumption, aggregate etc. and macro property.The cement-based material coefficient of heat conductivity is along with the change of its match ratio etc. and change, experimental measurement is more difficult, existing achievement in research lacks the systematic study to the cement-based material coefficient of heat conductivity, due to reasons such as starting material, match ratio, environmental baseline, testing apparatus and method of testing and testing crew operative techniquies, the thermal parameters discreteness that provides is larger simultaneously.
The overall performance of compound substance depends on performance, geometric shape and the topological structure of composition material.Cement paste is the porous media material of very complex, and its component is various, the solid, liquid, gas three-phase coexistence, and disorder distribution, the range scale of these species distribution is wide, and from the nanometer to the micron, millimeter has a distribution, and it forms structure and at hydration process, larger variation occurs.Multi-dimension analogy method can be considered the composition material feature on different scale, realization is from the material property simulation of microcosmic-thin sight the-macroscopic view, set up the relation between material constituent performance, micromechanism and macro property, and fundamentally explain the change mechanism of material macro property, this is for promoting that investigation of materials is significant.
Summary of the invention
Technical matters to be solved by this invention is to overcome the prior art deficiency, provide a kind of sclerosis Portland cement only to starch coefficient of heat conductivity multi-scale prediction method, essential attribute according to starting material component and hydrated product, based on the cement paste micromechanism, adopt the coefficient of heat conductivity of the clean slurry of multiple dimensioned and homogenization method prediction sclerosis Portland cement, thereby provide coefficient of heat conductivity parameter accurately for mechanics, deformation performance research and the Numerical Simulation Analysis of cement-based material.
Sclerosis Portland cement of the present invention is starched coefficient of heat conductivity multi-scale prediction method only, comprises the following steps:
Steps A, the clean slurry of the Portland cement that will harden are divided into different scale according to microstructure, and each yardstick comprises different typical phases;
Step B, obtain the sclerosis Portland cement only starch the volumn concentration of each phase in each yardstick;
Step C, from smallest dimension, adopt upwards progressively homogenising and generalized self-consistent method, calculate the coefficient of heat conductivity that the sclerosis Portland cement is starched each yardstick only; Wherein, homogenising adopts compound in twos mode, and is specific as follows:
Get two kinds respectively as matrix be mingled with and carry out compoundly from the phase that participates in homogenising, and calculate the coefficient of heat conductivity of its compound phase that is combined into; Respectively as matrix be mingled with and carry out compoundly, and calculate the coefficient of heat conductivity of its compound phase that is combined into above-mentioned compound phase and other a kind of phase that participates in homogenising; The rest may be inferred, all completes compoundly until participate in the phase of homogenising, and the coefficient of heat conductivity of the compound phase that obtains at last is the coefficient of heat conductivity of the phase after homogenising; Wherein, the coefficient of heat conductivity of the compound phase of two kinds of phases calculates according to following formula:
k eff = k m [ 1 + 3 v e v m + 3 k m k e - k m ] ,
In formula, k effBe the coefficient of heat conductivity of compound phase, k m, v mBe respectively coefficient of heat conductivity and the volumn concentration of matrix, k e, v eBe respectively the coefficient of heat conductivity and the volumn concentration that are mingled with;
The coefficient of heat conductivity of the out to out after homogenising is the coefficient of heat conductivity of the clean slurry of sclerosis Portland cement.
As preferred version of the present invention, described in steps A, partition of the scale is specific as follows: be divided into three scales from low to high: yardstick I, yardstick II, yardstick III; The yardstick I comprises not hydrated cement groups of grains phase of these four kinds of tricalcium silicates, dicalcium silicate, tetra calcium aluminoferrite, tricalcium aluminate, and calcium hydroxide, hydrated calcium silicate, Fu Tiexiang, these four kinds of hydrated product group phases of other hydrated product; The yardstick II comprises the not hydrated cement particle after yardstick I homogenising, and the hydrated product after yardstick I homogenising; The yardstick III comprises the cement slurry solid phase after yardstick II homogenising, and capillary water and pore space.
Compared to existing technology, the present invention has following beneficial effect:
The present invention is based on the essential characteristic of cement-based material coefficient of heat conductivity, it is the essential attribute of composition material component and hydrated product, and micromechanism, set up the sclerosis Portland cement with actual physics meaning parameter and only starched the coefficient of heat conductivity forecast model, thereby cement paste micromechanism and macro property are set up contact, and cement-based material macro property influence factor is many from having solved in essence, the discrete large problem of test figure.By the inventive method, can more conveniently obtain the coefficient of heat conductivity of the clean slurry of Portland cement that hardens, and not need to carry out actual measurement by a cover proving installation.
Description of drawings
Fig. 1 starches the partition of the scale schematic diagram only for the sclerosis Portland cement;
Fig. 2 is the effective thermal conductivity model schematic diagram of heat transfer medium.
Embodiment
Below in conjunction with accompanying drawing, technical scheme of the present invention is elaborated:
The present invention is based on Microstructure of Cement-based Material the coefficient of heat conductivity of the clean slurry of sclerosis Portland cement is studied, by the cement paste micromechanism with forms the phase essential attribute and set up the multi-scale prediction model that the Portland cement that hardens is starched coefficient of heat conductivity only.
Cement-based material life period, the intrinsic multiple dimensioned characteristic in space, for example high and low density hydrated calcium silicate is at nanoscale, and the hydrated products such as calcium hydroxide, hydrated cement particle, large pore be not at micro-meter scale, cement paste is at mm-scale.Multi-scale method considers that the space across features such as the mechanics of materials of yardstick, distortion, is important method and the technology of finding the solution the complicated mechanics problems of various materials.Wherein, homogenization theory has advantages of that as a kind of effective multiscale simulation method theory is rigorous, be easy to Numerical Implementation material macro equivalent performance, is the important method of composite Materials Design, performance prediction and structure optimization.At hydrated calcium silicate, calcium hydroxide, not on the large mineral component yardstick of hydrated cement particle four, their coefficient of heat conductivity is the build-in attribute of these phases, with conditional independences such as water cement ratio, the length of times.Adopt multiple dimensioned and homogenization method, in conjunction with the micromechanism of the clean slurry of hardened cement, can be from predicting in essence its heat conductivility.
The inventive method specifically comprises the following steps:
Steps A, the clean slurry of the Portland cement that will harden are divided into different scale according to microstructure, and each yardstick comprises different typical phases.
Can adopt different partition of the scale modes according to actual conditions when carrying out partition of the scale, the preferred following partition of the scale mode (as shown in Figure 1) of the present invention: be divided into three scales from low to high: yardstick I, yardstick II, yardstick III; The yardstick I comprises not hydrated cement groups of grains phase of these four kinds of tricalcium silicates, dicalcium silicate, tetra calcium aluminoferrite, tricalcium aluminate, and calcium hydroxide, hydrated calcium silicate, Fu Tiexiang, these four kinds of hydrated product group phases of other hydrated product; The yardstick II comprises the not hydrated cement particle after yardstick I homogenising, and the hydrated product after yardstick I homogenising; The yardstick III comprises the cement slurry solid phase after yardstick II homogenising, and capillary water and pore space.Adopt this kind partition of the scale method, tricalcium silicate, dicalcium silicate, tetra calcium aluminoferrite, tricalcium aluminate, calcium hydroxide, hydrated calcium silicate, Fu Tie equate that the coefficient of heat conductivity of basic phase can adopt existing experimental data or inverting value, is convenient to subsequent treatment.
Step B, obtain the sclerosis Portland cement only starch the volumn concentration of each phase in each yardstick.
in each yardstick, the volumn concentration of each phase can (for example be obtained by test, the environmental scanning electronic microscope test), perhaps by Powers model (Powers T.C., Brownyard T.L.Studies of the Physical Properties of Hardened Portland Cement Paste.Part5.Studies of the Hardened Paste by Means of Specific-Volume Measurements[J] .Journal of American Concrete Institute, 1947, 18 (6): 669-711.) or Jennings-Tennis model (Jennings H.M., Tennis P.D.Model for the Developing Microstructure in Portland Cement Pastes[J] .Journal of the American Ceramic Society, 1994, 7 (12): 3161-3172.) or HYMOSTRC model (an Breugel K.Simulation of hydration and formation of structure in hardening cement-based materials, PhD thesis, Delft University of Technology, Delft, 1991.) calculate.
Step C, from smallest dimension, adopt upwards progressively homogenising and generalized self-consistent method, calculate the coefficient of heat conductivity that the sclerosis Portland cement is starched each yardstick only; Wherein, homogenising adopts compound in twos mode, and is specific as follows:
Get two kinds respectively as matrix be mingled with and carry out compoundly from the phase that participates in homogenising, and calculate the coefficient of heat conductivity of its compound phase that is combined into; Respectively as matrix be mingled with and carry out compoundly, and calculate the coefficient of heat conductivity of its compound phase that is combined into above-mentioned compound phase and other a kind of phase that participates in homogenising; The rest may be inferred, all completes compoundly until participate in the phase of homogenising, and the coefficient of heat conductivity of the compound phase that obtains at last is the coefficient of heat conductivity of the phase after homogenising; Wherein, the coefficient of heat conductivity of the compound phase of two kinds of phases calculates according to following formula:
k eff = k m [ 1 + 3 v e v m + 3 k m k e - k m ] ,
In formula, k effBe the coefficient of heat conductivity of compound phase, k m, v mBe respectively coefficient of heat conductivity and the volumn concentration of matrix, k e, v eBe respectively the coefficient of heat conductivity and the volumn concentration that are mingled with.
The concrete derivation of above-mentioned formula is as follows:
According to the definition of continuous medium Micromechanics compound substance effective performance, the coefficient of heat conductivity of material and thermograde tensor, heat flow density are relevant.For isotropic material heterogeneous, the coefficient of heat conductivity of homogenising can be expressed as formula (1):
k eff = q → H → - - - ( 1 )
In formula, k effBe the coefficient of heat conductivity of material homogenization,
Figure BDA00002782919600043
Be the heat flow density tensor,
Figure BDA00002782919600044
Be the thermograde tensor.
According to matrix shown in Figure 2-being mingled with system carries out homogenization, need to obtain be mingled with, substrate temperature field distribution function T e, T m
Temperature governing equation is:
▽ 2T e=00≤r≤a
▽ 2T m=0a≤r≤b
▽ 2T eff=0b≤r≤∞ (2) temperature boundary condition is:
T e = T m - k m C ( ∂ T m ∂ r ) r = a At border r=a
k m ( ∂ T m ∂ r ) r = a = k e ( ∂ T e ∂ r ) r = a At border r=a(3)
T eff=T mAt border r=b
k m ( ∂ T m ∂ r ) r = b = k eff ( ∂ T eff ∂ r ) r = b At border r=b
Figure BDA00002782919600054
In border r → ∞ (4) formula, k effFor treating the hot coefficient of differentiate,
Figure BDA00002782919600055
Be heat flow density, C be mingled with and matrix between heat transfer coefficient.
Try to achieve temperature field function T by formula (2), (3), (4) e, T mAfter, the substitution following formula:
H → = - ▿ ( T e + T m ) - - - ( 5 )
And then will
Figure BDA00002782919600057
Substitution formula (1) can get the coefficient of heat conductivity after hardened cement is starched two kinds of phase homogenising of certain yardstick only:
k eff = k m [ 1 + 3 v e - ( k m Ca ) 3 v e · k e k e - k m v m + 3 k m k e - k m + k m Ca ( 2 + v e ) k e k e - k m ] - - - ( 6 )
Further, do not consider matrix-be mingled with thermal resistance effect, namely get C for infinitely great, formula (6) can be reduced to:
k eff = k m [ 1 + 3 v e v m + 3 k m k e - k m ] - - - ( 7 )
When carrying out compound in twos homogenising, the compound order of each phase and matrix and the selection that is mingled with can be set according to actual conditions.In this embodiment, in the yardstick I, the homogenising of hydrated cement particle is not specifically in accordance with the following methods: take tetra calcium aluminoferrite as matrix, tricalcium aluminate for be mingled with carry out compound for the first time; As being mingled with, as matrix carry out for the second time compound with dicalcium silicate with the compound phase after compound for the first time; As being mingled with, carry out compoundly for the third time with the compound phase after compound for the second time as matrix with tricalcium silicate, namely obtain the coefficient of heat conductivity of the not hydrated cement Particle Phase after homogenising.
In the yardstick I, the homogenising of hydrated product specifically in accordance with the following methods: for being mingled with, it is compound for the first time that Fu Tiexiang is that matrix carries out with other hydrated products; As being mingled with, as matrix carry out for the second time compound with hydrated calcium silicate with the compound phase after compound for the first time; As matrix, carry out compoundly for the third time with calcium hydroxide as being mingled with the compound phase after compound for the second time, namely obtain the coefficient of heat conductivity of the hydrated product phase after homogenising.
In the yardstick II, the homogenising of cement slurry solid phase is specifically in accordance with the following methods: with the not hydrated cement Particle Phase after yardstick I homogenising for being mingled with, hydrated product after the yardstick I homogenising carries out compoundly as matrix mutually, namely obtains the coefficient of heat conductivity of the cement slurry solid phase after homogenising.
The homogenising of yardstick III is specifically in accordance with the following methods: the cement slurry solid phase after the yardstick II homogenising is as matrix, with capillary water for be mingled with carry out compound; Then with resulting compound phase as matrix, carry out compoundly with the pore space as being mingled with, namely obtain the coefficient of heat conductivity of the cement slurry after homogenising.
The coefficient of heat conductivity of the yardstick III after homogenising is the coefficient of heat conductivity of the clean slurry of sclerosis Portland cement.
Adopt different match ratios, the cement paste mixture of variety classes cement, repeating step B～step C can obtain the coefficient of heat conductivity of the clean slurry of hardened cement of different mixture ratio.
In order to verify the effect of the inventive method, utilize the inventive method prediction to adopt that P.O52.5 cement, water cement ratio are 0.35, curing temperature is the coefficient of heat conductivity of the clean slurry of sclerosis Portland cement of 20.0 ℃, and be analyzed with the trial value of actual measurement.Test situation is specific as follows:
1, profile test
1.1 test starting material
The cement south of the River-little wild field board P.O52.5 portland cement, its main oxides component concentration such as table 1.
Table 1 cement main oxides component concentration
Figure BDA00002782919600061
1.2 testing program
Sample dimensions is 150mm * 150mm * 300mm, and the grout match ratio of employing sees Table 2.Build and completely rapidly test specimen is moved into that standard curing is indoor carries out maintenance afterwards, the thermal conductivity value of the clean slurry of hardened cement was measured in maintenance in 28 days afterwards.
Each material usage in table 2 grout
Figure BDA00002782919600062
Figure BDA00002782919600071
The coefficient of heat conductivity data of the basic phase that adopts when adopting the inventive method to carry out the coefficient of heat conductivity prediction see Table 3.
The coefficient of heat conductivity value of each phase of table 3 (kJ/ (mh ℃))
2, interpretation of result
Water cement ratio is that 0.35 hardened cement is only starched coefficient of heat conductivity to measure mean values three times be 3.78kJ/ (mh ℃), and the calculated value that adopts Forecasting Methodology of the present invention to obtain is 3.94kJ/ (mh ℃), and error is 4.22%.
Can find out to have the good goodness of fit between predicted value and measured value from experimental result, illustrate that forecast model that the present invention proposes can characterize preferably hardened cement and only starch coefficient of heat conductivity.
The present invention only starches micromechanism according to cement, hydrated product essential attribute and hardened cement and sets up hardened cement and only starch coefficient of heat conductivity multi-scale prediction model building method, thereby set up the contact between material microstructure and macro property, this is that prior art is difficult to realize.

Claims (7)

1. the sclerosis Portland cement is starched coefficient of heat conductivity multi-scale prediction method only, it is characterized in that, comprises the following steps:
Steps A, the clean slurry of the Portland cement that will harden are divided into different scale according to microstructure, and each yardstick comprises different typical phases;
Step B, obtain the sclerosis Portland cement only starch the volumn concentration of each phase in each yardstick;
Step C, from smallest dimension, adopt upwards progressively homogenising and generalized self-consistent method, calculate the coefficient of heat conductivity that the sclerosis Portland cement is starched each yardstick only; Wherein, homogenising adopts compound in twos mode, and is specific as follows:
Get two kinds respectively as matrix be mingled with and carry out compoundly from the phase that participates in homogenising, and calculate the coefficient of heat conductivity of its compound phase that is combined into; Respectively as matrix be mingled with and carry out compoundly, and calculate the coefficient of heat conductivity of its compound phase that is combined into above-mentioned compound phase and other a kind of phase that participates in homogenising; The rest may be inferred, all completes compoundly until participate in the phase of homogenising, and the coefficient of heat conductivity of the compound phase that obtains at last is the coefficient of heat conductivity of the phase after homogenising; Wherein, the coefficient of heat conductivity of the compound phase of two kinds of phases calculates according to following formula:
k eff = k m [ 1 + 3 v e v m + 3 k m k e - k m ] ,
In formula, k effBe the coefficient of heat conductivity of compound phase, k m, v mBe respectively coefficient of heat conductivity and the volumn concentration of matrix, k e, v eBe respectively the coefficient of heat conductivity and the volumn concentration that are mingled with;
The coefficient of heat conductivity of the out to out after homogenising is the coefficient of heat conductivity of the clean slurry of sclerosis Portland cement.
2. the Portland cement that hardens is as claimed in claim 1 starched coefficient of heat conductivity multi-scale prediction method only, it is characterized in that, described in steps A, partition of the scale is specific as follows: be divided into three scales from low to high: yardstick I, yardstick II, yardstick III; The yardstick I comprises not hydrated cement groups of grains phase of these four kinds of tricalcium silicates, dicalcium silicate, tetra calcium aluminoferrite, tricalcium aluminate, and calcium hydroxide, hydrated calcium silicate, Fu Tiexiang, these four kinds of hydrated product group phases of other hydrated product; The yardstick II comprises the not hydrated cement particle after yardstick I homogenising, and the hydrated product after yardstick I homogenising; The yardstick III comprises the cement slurry solid phase after yardstick II homogenising, and capillary water and pore space.
3. the Portland cement that hardens is as claimed in claim 2 starched coefficient of heat conductivity multi-scale prediction method only, it is characterized in that, in the yardstick I, the homogenising of hydrated cement particle is not specifically in accordance with the following methods: take tetra calcium aluminoferrite as matrix, tricalcium aluminate for be mingled with carry out compound for the first time; As being mingled with, as matrix carry out for the second time compound with dicalcium silicate with the compound phase after compound for the first time; As being mingled with, carry out compoundly for the third time with the compound phase after compound for the second time as matrix with tricalcium silicate, namely obtain the coefficient of heat conductivity of the not hydrated cement Particle Phase after homogenising.
4. the Portland cement that hardens is as claimed in claim 2 starched coefficient of heat conductivity multi-scale prediction method only, it is characterized in that, in the yardstick I, the homogenising of hydrated product specifically in accordance with the following methods: for being mingled with, it is compound for the first time that Fu Tiexiang is that matrix carries out with other hydrated products; As being mingled with, as matrix carry out for the second time compound with hydrated calcium silicate with the compound phase after compound for the first time; As matrix, carry out compoundly for the third time with calcium hydroxide as being mingled with the compound phase after compound for the second time, namely obtain the coefficient of heat conductivity of the hydrated product phase after homogenising.
5. the Portland cement that hardens is as claimed in claim 2 starched coefficient of heat conductivity multi-scale prediction method only, it is characterized in that, in the yardstick II, the homogenising of cement slurry solid phase is specifically in accordance with the following methods: with the not hydrated cement Particle Phase after yardstick I homogenising for being mingled with, hydrated product after the yardstick I homogenising carries out compoundly as matrix mutually, namely obtains the coefficient of heat conductivity of the cement slurry solid phase after homogenising.
6. the Portland cement that hardens is as claimed in claim 2 starched coefficient of heat conductivity multi-scale prediction method only, it is characterized in that, the homogenising of yardstick III is specifically in accordance with the following methods: the cement slurry solid phase after the yardstick II homogenising is as matrix, with capillary water for be mingled with carry out compound; Then with resulting compound phase as matrix, carry out compoundly with the pore space as being mingled with, namely obtain the coefficient of heat conductivity of the cement slurry after homogenising.
7. the Portland cement that hardens is as claimed in claim 1 starched coefficient of heat conductivity multi-scale prediction method only, it is characterized in that, described sclerosis Portland cement starches only that in different scale, the volumn concentration of each phase is obtained by test, perhaps calculated by the Powers model, perhaps calculated by the Jennings-Tennis model, perhaps calculated by the HYMOSTRC model.
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Application publication date: 20130522