CN107602030B - Early-strength cement-based phase change energy storage mortar and preparation method thereof - Google Patents
Early-strength cement-based phase change energy storage mortar and preparation method thereof Download PDFInfo
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Abstract
The invention discloses early-strength cement-based phase change energy storage mortar which comprises the following components in percentage by mass: 67.8-72.7% of phase change energy storage mortar base material, 10.9-17.0% of shape-stabilized phase change material and 15.2-16.4% of mixing water, wherein the sum of the mass percentages of the components is 100%; the invention also discloses a preparation method of the early strength type cement-based phase change energy storage mortar, which comprises the steps of weighing the phase change energy storage mortar base material, the shape-stabilized phase change material and the mixing water according to the proportion, pouring the mixture into a clay mortar stirrer, stirring to obtain the early strength type cement-based phase change energy storage mortar material which is uniformly mixed, pouring the early strength type cement-based phase change energy storage mortar material into a test mold for molding, and curing to a specified age under standard conditions to obtain the early. The early strength type cement-based phase change energy storage mortar solves the problems of low strength increase speed and poor heat storage capacity of the phase change energy storage mortar in the prior art.
Description
Technical Field
The invention belongs to the technical field of civil engineering materials, relates to early-strength cement-based phase-change energy storage mortar, and further relates to a preparation method of the energy storage mortar.
Background
Phase change energy storage materials have become a research hotspot in the field of building energy-saving materials, wherein solar heating buildings are one of the fields of phase change materials with the most application value in the building industry. The phase change material is reasonably applied to the solar building envelope structure, and can improve the heat storage and heat regulation capacity of the building, thereby improving the indoor thermal environment quality of the building and reducing the building energy consumption, and having the performance advantages which cannot be compared with the traditional building material. The cement concrete and the cement mortar are the building materials with the largest consumption in the building, so that the phase-change material is compounded with the cement-based material, and the phase-change material is more convenient to be widely applied to the building; the low-melting-point phase-change paraffin has the advantages of wide phase-change temperature, high energy storage density, good chemical stability, no supercooling and phase separation phenomena, wide raw material source, low price and the like, and is often used for preparing a cement-based phase-change composite material, but the phase-change paraffin is a solid-liquid phase-change material and is easy to leak in the using process. In order to solve the paraffin leakage problem of cement-based phase change concrete, students propose some creative methods, such as using porous steel slag coarse aggregate and porous ceramsite to adsorb a phase change material as concrete aggregate, and solving the leakage problem of the phase change paraffin; the cement mortar is one of the largest building materials in the building, has wide application field and flexible application mode, so that the phase change material and the cement-based mortar are compounded to prepare the phase change energy storage mortar, and the phase change material can be widely applied to the building more conveniently; however, the disclosed method for solving the phase change paraffin leakage based on the porous coarse aggregate cannot be directly adopted for the phase change energy storage mortar without the coarse aggregate. In addition, the current phase change energy storage mortar mainly adopts general portland cement as a cementing material, the early strength of the cement is low, the strength development is slow, the mechanical property of the phase change energy storage mortar is not ideal, and particularly, when the mixing amount of the phase change material is increased, the mechanical property of the phase change mortar is remarkably reduced. Generally, the cement-based phase change energy storage mortar technology in China is mostly in the experimental research stage, and the application in practical engineering is very limited. At present, the technical defects of the cement-based phase change energy storage mortar mainly exist in the following aspects:
(1) the preparation process of the shape-stabilized phase-change material is complex and easy to leak
In order to prevent the paraffin from leaking in the solid-liquid phase change process, the phase-change paraffin needs to be subjected to shaping treatment. Document 1 "phase change perlite process research and phase change mortar temperature control simulation" (qian li jiao, zhang xiong, songzhi, silicate academic report, 2013(7): 987-. Document 2, "chinese patent No. CN 104446238A", discloses a ternary composite paraffin/vitrified microsphere phase change energy storage mortar and a preparation method thereof, in the method, on the basis of realizing that vitrified microspheres adsorb liquid paraffin by using vacuum equipment, a styrene-acrylic emulsion is used to perform secondary packaging on vitrified microspheres containing a phase change material, thereby effectively solving the problem of leakage of the liquid paraffin, but the method has a complex process and high material preparation cost. Document 3, Yan all-in-one, Horan, Zhangin, building energy saving, 2011(9): 42-46), discloses a preparation method of a shape-stabilized phase change material by blending high-density polyethylene and paraffin, and the method utilizes a space network structure formed by cooling the high-density polyethylene from a molten state to normal temperature to package and wrap the paraffin. However, it is not difficult to find from the research results disclosed in document 4 "thermal properties of shaped phase change material" (Qinpeng, Zhang Yin Ping, Yan Rui, etc.. Qing Hua university school newspaper (Nature science edition), 2003,43(6): 833-. However, the preparation method of the shaping phase change material by blending and melting low-density polyethylene and paraffin is not reported in public, and one important reason is that the low-density polyethylene has low strength, so that the strength of the shaping phase change material is reduced, and the strength of the cement-based energy storage mortar is easily reduced remarkably, thereby affecting the engineering application of the cement-based energy storage mortar.
(2) The phase-change energy-storage mortar has low strength and slow strength development
The strength development speed of the phase change energy storage mortar is an important factor influencing the engineering application effect, but the strength of the shape-stabilized phase change material is far lower than that of fine aggregate (sand), so the strength of the phase change energy storage mortar is reduced along with the increase of the content of the shape-stabilized phase change material, and the strength of the phase change energy storage mortar is increased more slowly. Document 5 "preparation of phase change energy storage mortar and its properties" (wandangshu, zhao ning. shenyang university journal (nature science edition), 2014,26(4): 311-. Document 6, "chinese patent No. CN 101144006 a", discloses a phase change energy storage mortar compounded by portland cement (P.O 42.5.5), fine aggregate, an additive, water, and a filler, and a preparation method thereof, but does not describe the strength of the mortar. Document 7, "experimental research on performance of composite phase change energy storage mortar" (shi wei, ai bin, hou jing peng.silicate report.2014, 33(5): 1004-. The published documents show that the existing cement-based phase change energy storage mortar uses general portland cement as a base material, and the general portland cement has the characteristics of low strength development speed, shrinkage in a hardening process and the like, so that the strength and the strength increase speed of the phase change energy storage mortar with large phase change material content and lacking of an aggregate supporting function are adversely affected. In order to meet the basic requirements on the strength of materials in engineering application, the content of the phase-change material in the existing cement-based phase-change energy storage mortar is difficult to increase greatly, which can cause adverse effects on the improvement of the heat storage capacity of the energy storage mortar, thereby restricting the wide application of the materials.
Disclosure of Invention
The invention aims to provide early-strength cement-based phase-change energy storage mortar, which solves the problems of slow strength increase speed and poor heat storage capacity of the phase-change energy storage mortar in the prior art.
The invention also aims to provide a preparation method of the early-strength cement-based phase-change energy-storage mortar.
The early-strength cement-based phase change energy storage mortar adopts the technical scheme that the early-strength cement-based phase change energy storage mortar comprises the following components in percentage by mass: 67.8-72.7% of phase change energy storage mortar base material, 10.9-17.0% of shape-stabilized phase change material and 15.2-16.4% of mixing water, wherein the sum of the mass percentages of the components is 100%.
The shape-stabilized phase change material comprises the following components in percentage by mass: 38.4% of low-density polyethylene, 57.7% of phase-change paraffin and 3.9% of flake graphite.
The phase change energy storage mortar matrix material comprises the following components in percentage by mass: 49.9 percent of quick hardening sulphoaluminate cement with the strength grade of 42.5, 49.9 percent of quartz sand, 0.03 percent of polycarboxylic acid high-efficiency water reducing agent, 0.11 percent of lithium carbonate and 0.06 percent of boric acid.
The fineness modulus of the quartz sand is 2.5-2.7.
The invention adopts another technical scheme that the preparation method of the early-strength cement-based phase change energy storage mortar is implemented according to the following steps:
step 1, weighing 67.8-72.7% of phase change energy storage mortar base material, 10.9-17.0% of shape-stabilized phase change material and 15.2-16.4% of mixed water according to the mass percentage sum of 100%, pouring the materials into a clay mortar stirrer, and stirring for 3-5min to obtain the early-strength cement-based phase change energy storage mortar material which is uniformly mixed;
and 2, pouring the early-strength cement-based phase change energy storage mortar material into a test mold for molding, and curing to a specified age under standard conditions to obtain the early-strength cement-based phase change energy storage mortar.
The preparation process of the phase change energy storage mortar matrix material comprises the following steps:
weighing 49.9% of quick-hardening sulphoaluminate cement with the strength grade of 42.5, 49.9% of quartz sand with the fineness modulus of 2.5-2.7, 0.03% of polycarboxylic acid high-efficiency water reducing agent, 0.11% of lithium carbonate and 0.06% of boric acid according to the mass percentage, pouring the materials into a cement mortar stirrer, stirring for 3-5min and uniformly mixing.
The preparation process of the shape-stabilized phase-change material comprises the following steps:
respectively weighing 38.4% of low-density polyethylene, 57.7% of phase-change paraffin and 3.9% of flake graphite by mass percent, heating and stirring to obtain a molten mass, crushing the condensed molten mass into granules, and sieving.
In the preparation process of the shape-stabilized phase change material, heating is carried out in an oil bath pool of a heat collection type magnetic stirrer, the heat collection type magnetic stirrer is adjusted to be in a low-speed stirring state, after the temperature is increased to 170-180 ℃, the low-speed stirring state is kept for 20-25min, then the high-speed stirring state is kept for 10-15min, a molten body is obtained, and the molten body is condensed at room temperature.
In the preparation process of the shape-stabilized phase-change material, a round-hole sieve with the diameter of 2.5mm is selected during sieving.
The invention has the beneficial effects that the early drought type cement-based phase change energy storage mortar is prepared by compounding the shape-stabilized phase change material, the phase change energy storage mortar matrix material and mixing water: the phase change material in the shape-stabilized phase change material is low-temperature phase change paraffin, the carrier material is low-density polyethylene (LDPE), and the low-density polyethylene has the advantages of low melting point, good ductility and flexibility and the like compared with high-density polyethylene and other materials, so that the shape-stabilized phase change material which is not easy to leak can be prepared by a simple melt blending method, excellent thermal properties are given to the early-strength cement-based phase change energy storage mortar, and particularly high phase change latent heat is provided, so that the functions of storing and releasing heat energy are realized; the phase-change energy-storage mortar matrix material is composed of rapid-hardening sulphoaluminate cement with the strength grade of 42.5, quartz sand, a water reducing agent, a setting accelerator and a retarder, and has the characteristics of high hydration speed, high early strength, stable increase of later strength and the like
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The early-strength cement-based phase change energy storage mortar comprises the following components in percentage by mass: 67.8-72.7% of phase change energy storage mortar base material, 10.9-17.0% of shape-stabilized phase change material and 15.2-16.4% of mixing water, wherein the sum of the mass percentages of the components is 100%.
The shape-stabilized phase change material comprises the following components in percentage by mass: 38.4% of low-density polyethylene, 57.7% of phase-change paraffin and 3.9% of flake graphite.
The phase change energy storage mortar matrix material comprises the following components in percentage by mass: 49.9 percent of quick hardening sulphoaluminate cement with the strength grade of 42.5, 49.9 percent of quartz sand, 0.03 percent of polycarboxylic acid high-efficiency water reducing agent, 0.11 percent of lithium carbonate and 0.06 percent of boric acid.
The fineness modulus of the quartz sand is 2.5-2.7.
The preparation method of the early strength type cement-based phase change energy storage mortar is implemented according to the following steps:
step 1, weighing 67.8-72.7% of phase change energy storage mortar base material, 10.9-17.0% of shape-stabilized phase change material and 15.2-16.4% of mixed water according to the mass percentage sum of 100%, pouring the materials into a clay mortar stirrer, and stirring for 3-5min to obtain the early-strength cement-based phase change energy storage mortar material which is uniformly mixed;
and 2, pouring the early-strength cement-based phase change energy storage mortar material into a test mold for molding, and curing to a specified age under standard conditions to obtain the early-strength cement-based phase change energy storage mortar.
The preparation process of the phase change energy storage mortar matrix material comprises the following steps:
weighing 49.9% of quick-hardening sulphoaluminate cement with the strength grade of 42.5, 49.9% of quartz sand with the fineness modulus of 2.5-2.7, 0.03% of polycarboxylic acid high-efficiency water reducing agent, 0.11% of lithium carbonate and 0.06% of boric acid according to the mass percentage, pouring the materials into a cement mortar stirrer, stirring for 3-5min and uniformly mixing.
The preparation process of the shape-stabilized phase-change material comprises the following steps:
respectively weighing 38.4% of low-density polyethylene, 57.7% of phase-change paraffin and 3.9% of flake graphite by mass percent, heating and stirring to obtain a molten mass, crushing the condensed molten mass into granules, and sieving.
In the preparation process of the shape-stabilized phase change material, heating is carried out in an oil bath pool of a heat collection type magnetic stirrer, the heat collection type magnetic stirrer is adjusted to be in a low-speed stirring state, after the temperature is increased to 170-180 ℃, the low-speed stirring state is kept for 20-25min, then the high-speed stirring state is kept for 10-15min, a molten body is obtained, and the molten body is condensed at room temperature.
In the preparation process of the shape-stabilized phase-change material, a round-hole sieve with the diameter of 2.5mm is selected during sieving.
Example 1:
step 1, weighing 49.9% of quick-hardening sulphoaluminate cement with the strength grade of 42.5, 49.9% of quartz sand with the fineness modulus of 2.5, 0.03% of polycarboxylic acid high-efficiency water reducing agent (powder), 0.11% of lithium carbonate and 0.06% of boric acid according to the mass percentage, pouring the materials into a cement mortar stirrer, stirring for 3min, and uniformly mixing to obtain dry powder of the phase-change energy-storage mortar matrix material;
respectively weighing 38.4% of low-density polyethylene, 57.7% of phase-change paraffin wax at 20 ℃ and 3.9% of flake graphite powder according to mass percent, pouring the weighed materials into a beaker, putting the beaker into an oil bath pool of a heat collection type magnetic stirrer for heating, setting the temperature of the heat collection type magnetic stirrer to be 170 ℃, adjusting the temperature of the heat collection type magnetic stirrer to be in a low-speed stirring state, keeping the temperature for 20min after the temperature is raised to 170 ℃, then adjusting the temperature to be in a high-speed stirring state for 10min to obtain a molten mass, mechanically crushing the molten mass into particles after the molten mass is condensed at room temperature, and sieving the particles through a round hole sieve of 2.5mm to obtain a dry powder of a shape-stabilized phase-change material;
respectively weighing 16.4% of mixing water, 72.7% of dry powder of a phase change energy storage mortar matrix material and 10.9% of dry powder of a shape-stabilized phase change material according to the mass percentage sum of 100%, sequentially pouring the materials into a mortar and sand mixer, and mixing for 3min to obtain an early-strength cement-based phase change energy storage mortar material which is uniformly mixed;
and 2, pouring the early-strength cement-based phase change energy storage mortar material into a test mold for molding, and curing to a specified age under standard conditions to obtain the early-strength cement-based phase change energy storage mortar.
Example 2:
step 1, weighing 49.9% of quick-hardening sulphoaluminate cement with the strength grade of 42.5, 49.9% of quartz sand with the fineness modulus of 2.6, 0.03% of polycarboxylic acid high-efficiency water reducing agent (powder), 0.11% of lithium carbonate and 0.06% of boric acid according to the mass percentage, pouring the materials into a cement mortar stirrer, stirring for 4min, and uniformly mixing to obtain dry powder of the phase-change energy-storage mortar matrix material;
respectively weighing 38.4% of low-density polyethylene, 57.7% of phase-change paraffin wax at 20 ℃ and 3.9% of flake graphite powder according to mass percent, pouring the weighed materials into a beaker, putting the beaker into an oil bath pool of a heat collection type magnetic stirrer for heating, setting the temperature of the heat collection type magnetic stirrer to be 175 ℃, adjusting the temperature of the heat collection type magnetic stirrer to be in a low-speed stirring state, keeping the temperature for 23min after the temperature is raised to be 175 ℃, then adjusting the temperature to be in a high-speed stirring state for 13min to obtain a molten mass, mechanically crushing the molten mass into particles after the molten mass is condensed at room temperature, and sieving the particles through a round hole sieve of 2.5mm to obtain a dry powder of a shape-stabilized phase-change material;
respectively weighing 15.8% of mixing water, 70.2% of dry powder of a phase change energy storage mortar matrix material and 14.0% of dry powder of a shape-stabilized phase change material according to the mass percentage sum of 100%, sequentially pouring the materials into a mortar and sand mixer, and mixing for 4min to obtain an early-strength cement-based phase change energy storage mortar material which is uniformly mixed;
and 2, pouring the early-strength cement-based phase change energy storage mortar material into a test mold for molding, and curing to a specified age under standard conditions to obtain the early-strength cement-based phase change energy storage mortar.
Example 3:
step 1, weighing 49.9% of quick-hardening sulphoaluminate cement with the strength grade of 42.5, 49.9% of quartz sand with the fineness modulus of 2.7, 0.03% of polycarboxylic acid high-efficiency water reducing agent (powder), 0.11% of lithium carbonate and 0.06% of boric acid according to the mass percentage, pouring the materials into a cement mortar stirrer, stirring for 5min, and uniformly mixing to obtain dry powder of the phase-change energy-storage mortar matrix material;
respectively weighing 38.4% of low-density polyethylene, 57.7% of phase-change paraffin wax at 20 ℃ and 3.9% of flake graphite powder according to mass percent, pouring the weighed materials into a beaker, putting the beaker into an oil bath pool of a heat collection type magnetic stirrer for heating, setting the temperature of the heat collection type magnetic stirrer to be 180 ℃, adjusting the temperature of the heat collection type magnetic stirrer to be in a low-speed stirring state, keeping the temperature for 25min after the temperature is raised to 180 ℃, then adjusting the temperature to be in a high-speed stirring state for 15min to obtain a molten mass, mechanically crushing the molten mass into particles after the molten mass is condensed at room temperature, and sieving the particles through a round hole sieve of 2.5mm to obtain a dry powder of a shape-stabilized phase-change material;
respectively weighing 15.2% of mixing water, 67.8% of dry powder of a phase change energy storage mortar matrix material and 17.0% of dry powder of a shape-stabilized phase change material according to the mass percentage sum of 100%, sequentially pouring the materials into a mortar and sand mixer, and mixing for 5min to obtain an early-strength cement-based phase change energy storage mortar material which is uniformly mixed;
and 2, pouring the early-strength cement-based phase change energy storage mortar material into a test mold for molding, and curing to a specified age under standard conditions to obtain the early-strength cement-based phase change energy storage mortar.
The following table shows the comparison of the properties of the early strength cement-based phase change energy storage mortar prepared in examples 1, 2 and 3.
Table 1 Performance of early strength type cement-based phase change energy storage mortar prepared in examples 1-3
As can be seen from Table 1, the compressive strength and the flexural strength of example 1 cured for 1 day were 9.3MPa and 3.1MPa, respectively, and 69.9% and 70.5% of those of example 1 cured for 28 days; the compressive strength and the flexural strength of the mixture after 3 days of curing are respectively 10.8MPa and 3.3MPa, which respectively reach 81.2 percent and 75.0 percent of the compressive strength and the flexural strength of the mixture after 28 days of curing, and the enthalpy value of the mixture in the example 1 reaches 11.2J/g; compared with the embodiment 1, the proportion of the materials in the embodiments 2 and 3 is changed, the content of the shape-stabilized phase-change material is mainly increased, and the content of other components is correspondingly reduced, but the strength test data of the embodiments 2 and 3 show that the embodiments 2 and 3 also have the performance characteristics of early strength and quick hardening, and the enthalpy value of the material is respectively improved by 26.8 percent and 56.3 percent compared with the embodiment 1 and reaches 14.2J/g and 17.5J/g; the performance parameters of the three embodiments are integrated, the 1d compressive strength is 5.58-9.26MPa, the 3d compressive strength is 6.51-10.78MPa, and the 28d compressive strength is 9.01-13.26 MPa.
According to the method, the shaping phase-change material, the phase-change energy storage mortar matrix material and the mixing water are compounded to prepare the early drought type cement-based phase-change energy storage mortar:
the phase change material in the shape-stabilized phase change material is low-temperature phase change paraffin wax at 20 ℃, the carrier material is low-density polyethylene (LDPE), and the low-density polyethylene has the advantages of low melting point, good ductility and flexibility and the like compared with materials such as high-density polyethylene, so that the shape-stabilized phase change material which is not easy to leak can be prepared by a simple melt blending method, excellent thermal properties are given to the early-strength cement-based phase change energy storage mortar, and particularly high phase change latent heat is provided, so that the functions of storing and releasing heat energy are realized;
the phase-change energy storage mortar matrix material is composed of rapid hardening sulphoaluminate cement with the strength grade of 42.5, quartz sand, a water reducing agent, a setting accelerator and a retarder, and has the characteristics of high hydration speed, high early strength, stable increase of later strength and the like.
Claims (4)
1. The early-strength cement-based phase change energy storage mortar is characterized by comprising the following components in percentage by mass: 67.8-72.7% of phase change energy storage mortar base material, 10.9-17.0% of shape-stabilized phase change material and 15.2-16.4% of mixing water, wherein the sum of the mass percentages of the components is 100%;
the shape-stabilized phase change material comprises the following components in percentage by mass: 38.4% of low-density polyethylene, 57.7% of phase-change paraffin and 3.9% of flake graphite;
the phase change energy storage mortar matrix material comprises the following components in percentage by mass: 49.9 percent of quick hardening sulphoaluminate cement with the strength grade of 42.5, 49.9 percent of quartz sand, 0.03 percent of polycarboxylic acid high-efficiency water reducing agent, 0.11 percent of lithium carbonate and 0.06 percent of boric acid.
2. The early strength cement-based phase change energy storage mortar of claim 1, wherein the fineness modulus of the quartz sand is 2.5-2.7.
3. The preparation method of the early-strength cement-based phase change energy storage mortar is characterized by comprising the following steps:
step 1, weighing 67.8-72.7% of phase change energy storage mortar base material, 10.9-17.0% of shape-stabilized phase change material and 15.2-16.4% of mixed water according to the mass percentage sum of 100%, pouring the materials into a cement mortar mixer, and stirring for 3-5min to obtain the early-strength cement-based phase change energy storage mortar material which is uniformly mixed;
the preparation process of the phase change energy storage mortar matrix material is as follows:
weighing 49.9% of quick-hardening sulphoaluminate cement with the strength grade of 42.5, 49.9% of quartz sand with the fineness modulus of 2.5-2.7, 0.03% of polycarboxylic acid high-efficiency water reducing agent, 0.11% of lithium carbonate and 0.06% of boric acid according to the mass percentage, pouring the materials into a cement mortar stirrer, stirring for 3-5min and uniformly mixing;
the preparation process of the shape-stabilized phase change material is as follows:
respectively weighing 38.4% of low-density polyethylene, 57.7% of phase-change paraffin and 3.9% of flake graphite according to the mass percentage, heating and stirring to obtain a molten mass, crushing the condensed molten mass into granules, and sieving;
in the preparation process of the shape-stabilized phase change material, heating in an oil bath pool of a heat collection type magnetic stirrer, adjusting the heat collection type magnetic stirrer to be in a low-speed stirring state, keeping the low-speed stirring state for 20-25min after the temperature is increased to 170-180 ℃, then adjusting to be in a high-speed stirring state for 10-15min to obtain a molten mass, and condensing the molten mass at room temperature;
and 2, pouring the early-strength cement-based phase change energy storage mortar material into a test mold for molding, and curing to a specified age under standard conditions to obtain the early-strength cement-based phase change energy storage mortar.
4. The preparation method of the early strength type cement-based phase change energy storage mortar according to claim 3, wherein a 2.5mm round hole sieve is selected during sieving in the preparation process of the shape-stabilized phase change material.
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