CN101096297A - Organic phase-change composite light-weight sintering ceramic particle and preparation method thereof - Google Patents
Organic phase-change composite light-weight sintering ceramic particle and preparation method thereof Download PDFInfo
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- CN101096297A CN101096297A CNA2006100521610A CN200610052161A CN101096297A CN 101096297 A CN101096297 A CN 101096297A CN A2006100521610 A CNA2006100521610 A CN A2006100521610A CN 200610052161 A CN200610052161 A CN 200610052161A CN 101096297 A CN101096297 A CN 101096297A
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Abstract
The invention relates to an organic phase-change material composite lightweight sintering ceramsite with phase-change thermoregulation function in the material science field, which encapsulates the organic phase-change material and the fire retarding agent and is made with the vacuum adsorption device which penetrates the organic phase-change material and the fire retarding agent in the internal pore space of the lightweight sintering ceramsite. The preparing method comprises the following steps: opening the air escape valve slowly after mixing the lightweight sintering ceramsite, the organic phase-change material and the fire retarding agent according to the proportion in the vacuum autoclave; reducing the vacuum degree to the atmosphere pressure in the autoclave; absorbing and penetrating the organic phase-change material and the fire retarding agent dissolved and encapsulated on the surface of the lightweight sintering ceramsite particle in the internal pore space of the lightweight sintering ceramsite; reducing the temperature; discharging; getting the organic phase-change material composite lightweight sintering ceramsite. The invention removes the mechanical property effect and fire prevention property effect of the building material, which guarantees the stability of high phase-change energy-storage heat capacity, the phase-change energy-storage skeletal material circulating work and penetrability resistance.
Description
Technical field
The present invention relates to building energy conservation and use the material field, relate in particular to organic phase-change composite light-weight sintering ceramic particle with phase-changing and temperature-regulating function and preparation method thereof.
Background technology
The energy consumption of China unit's floor area of building is up to 3 times of the close developed country of weather condition, and 95% buildings belongs to high energy consumption building, about 30% of building energy consumption account whole society total energy consumption.Along with China's economic construction and real estate rapid growth, the China that resource scarcity, pollution are increasingly sharpened brings bigger electric power burden.Therefore, building energy conservation is a very important and urgent problem to China.
The thermal energy storage technology can be alleviated energy supply and demand unmatched contradiction on time and intensity of buildings, and the heating of balance buildings and air conditioner load improve the comfort level of living environment greatly.The heat application memory technology not only can be dwindled the scale of Cooling and Heat Source, saves initial cost, and because the network load time-of-use tariffs are divided the implementation of meter system, the heat application memory technology can also reduce the working cost of heating, air-conditioning system.In addition, the thermal energy storage technology also is effectively to store, utilize the important channel of low-cost clean energies such as sun power in the heating, air-conditioning system at buildings, helps environmental protection, energy-conservation.
The effective thermal energy storage of the application need of sun power, and phase change material (phase change material, a large amount of latent heats of phase change of required absorption and release have just in time satisfied this demand when PCM) undergoing phase transition, and the research and development of New-type phase change type energy-saving building materials are the focus and the forefront direction of current building energy saving field with using.
The ideal energy-storage materials of construction must meet the following conditions: 1) transformation temperature is near 20～26 ℃ of the comfort levels of human body; 2) have enough big latent heat of phase change and heat conductivity; 3) expand during phase transformation or shrinkability little; 4) reversibility of phase transformation will be got well; 5) nontoxicity, non-corrosiveness, nothing degraded, free from extraneous odour; 6) the making raw material is cheap and easy to get.Early stage research mainly concentrates on the inorganic hydrated salt that cheaply is easy to get, but since its serious mistake cold with separate out problem, the phase transformation material of construction recycles the back energy storage and reduces with transformation temperature scope fluctuation very greatly greatly, has limited its practical application in building material field greatly.For fear of the problems referred to above of inorganic phase-changing material, people have focused on research emphasis the anhydrous organism of low volatility again, as: polyoxyethylene glycol, lipid acid and paraffin derivative etc.Although their price is higher than common salt hydrate, and the hot storage capacity of unit is low, the physical and chemical performance that it is stable, and good thermal behavior and adjustable transformation temperature all make it have broad application prospects.
In in the past 20 years, the phase change material of containerization is applied to field of solar energy by market, but because its area that contacts with environment when phase transformation is too little, is not very effective and make its transmission ofenergy.On the contrary, the common building material conducts heat but for each regional passive type of buildings enough big contact area is provided, thereby has caused that people more pay attention to.The combination of research phase change material and common building material, the consistency of research phase change material and common building material and mix afterwards that heat accumulation, heat transfer, machinery and the fire performance of material are the key technical problems that PCM is applied to material of construction.
Current, the combination technology of PCM and base material mainly contains 3 kinds: directly add, immerse and encapsulation.Directly addition method is convenient to control the add-on of PCM, and immersing rule can handle the finished product material of construction.Encapsulation is exactly to comprise PCM with differing materials, shape and big or small capsule before directly adding.Encapsulation technology has two kinds of main method, and the one, little encapsulation technology, the particle with little spheric or rod is encapsulated in the thin high-molecular polythene film exactly, and then adds base material; The 2nd, big encapsulation technology is included in PCM bigger container such as test tube, spheroid, panel etc. exactly.These containers both can also can add in the building materials directly as heat exchanger.These technology or can influence the mechanical property of building materials perhaps have influence on the fire resistance of product, and practical application foreground causes anxiety.
And utilize " two-step approach " technology, promptly at first make the phase-change accumulation energy aggregate of high stable high heat capacity, adopt the phase-change accumulation energy aggregate again, prepare various types of phase-change accumulation energy concrete building materials with the technology of preparing of normal concrete, be the combination technology of most promising PCM and construction substrate, wide application prospect will be arranged.
Someone has applied for that (application number is a kind of organosilicon by name: CN03153207.1), belong to building material field from temperature adjustment energy-conserving and environment-protective materials for wall.Building materials and chemical industry are combined, utilize composite principle, by self heat change mechanism frequently, summer, 2-3 ℃ of room temperature decline reduced air-conditioning 50% power consumption by the body of wall physical modification of absorbing heat.By accumulation of heat, improve Greenhouse effect in the winter time.Easy construction, the new building of widespread use is decorated, and thoroughly overcomes cracking of wall surface, dewfall, peeling, congenital defect problem such as mouldy, and has fine sterilization, soundproof effect, improves residential amenity and function class.Its raw materials used proportioning is (kg/m3) diatomite 20-25; Brucite 12-15; Starch 4-6; Pyrophyllite; Chitosan; Organic silicon emulsion; Mierocrystalline cellulose C cetylate 5-7; Paraffin 5-8; Float pearl; Sodium hydroxide.It has certain effect of regulating the room temperature but DeGrain, unsuitable large-scale industrial production.The somebody has applied for that (application number is a kind of a kind of patent from temperature adjustment construction wall plastering mortar material and preparation method thereof by name: CN200310112982.5), providing a kind of can not ooze out, frost-free, its stable performance from temperature adjustment construction wall plastering mortar material and preparation method thereof.Technical scheme is: a kind of from temperature adjustment construction wall plastering mortar material, it is characterized in that: described mortar material contains the batching of following weight per-cent: phase change composite material 5～15%; Building sand 20～50%, gelling material 30～50%, anti-bacterium mildewproof additive 1～5%, surplus is a water.Its preparation method is: earlier with above-mentioned building sand, gelling material, anti-bacterium mildewproof additive, after surplus is the water thorough mixing, add phase change composite material again, be directly used in the building operation metope after mixing; Its production method is simple, and is time saving and energy saving, and the fluctuating range of room temperature reduces by 4～6 ℃, and air-conditioning reduces more than 2 hours/day duration of service, and cost is low, and is easy to spread and implement.But the work-ing life of its regulation range and material is lower, is difficult to the scale of beating and promotes.The somebody has applied for accumulation of energy material of construction by name and preparation method thereof, and (number of patent application is: CN200410041384.8), mixture and building substrate material that it is made up of capric acid, lauric acid are composited, and capric acid and lauric acid are pressed mass ratio (1～8): 1.Preparation method of the present invention heats capric acid and lauric acid respectively, treat that they melt fully after, mix to form a kind of capric acid and lauric eutectic mixture by above-mentioned proportional range; Again this eutectic mixture is heated to complete melted state, is compound in the building substrate material, form a kind of accumulation of energy material of construction.In building energy saving field, compound by materials for wall and energy-accumulation material, can increase the temperature regulation ability of buildings, reach energy-conservation and comfortable purpose.Attemperation (18-25 ℃) in transformation temperature of this energy-accumulation material (19-24 ℃) and the room matches, and latent heat of phase change higher (120-150kJ/kg) did not have the cold-peace phenomenon of phase separation, nontoxic, non-corrosiveness, stable performance, good reproducibility.Though it has solved the shortcoming that is separated, the hybrid mode of its phase change material and building base-material still is simple the mixing, and its effect is relatively poor.
Summary of the invention
The purpose of this invention is to provide a kind ofly have that complex phase microstructure, stability are good, phase-change accumulation energy thermal capacitance height, technology is simple, cost is low, the phase-change accumulation energy aggregate of easy enforcement is organic phase-change composite light-weight sintering ceramic particle and preparation method thereof.
Above-mentioned radix purpose of the present invention is achieved by technical scheme once:
A kind of organic phase change material composite light-weight sintering ceramic particle, it is characterized in that it is made up of light-weight sintering ceramic particle, organic phase change material and fire retardant, this three's mass ratio is 1: 0.5～5: 0.1～0.5, and described organic phase change material and fire retardant are in the light-weight sintering ceramic particle.Described light-weight sintering ceramic particle is that a kind of unit weight is 100～400kg/m
3The ceramic honeycombed grain aggregate that makes through sintering process, described organic phase change material is generally the mixture that organosilicon or n-butyl stearate, organic resin emulsion, solidifying agent are formed, it can also be the material that lauryl alcohol or tetradecyl alcohol and mineral substance are formed, can also be polyvinyl alcohol, paraffin, n-hexadecane, n-heptadecane etc., described fire retardant purpose is to prevent that organic phase change material from burning under hot conditions, is generally common material of construction usefulness fire retardant such as boric acid, borax, ammonium phosphate, phosphoric acid, halogenation stone sodium, halogenous alkane etc.
As preferably, described organic phase change material is that fusing point is one or more in 15～40 ℃ polyoxyethylene glycol, lipid acid, paraffin or the paraffin derivative.Preferred transformation temperature is at 20～28 ℃ above-mentioned materials.
As preferably, described fire retardant is one or more in ammonium phosphate, phosphoric acid or the Halogen alkane.
As preferably, described light-weight sintering ceramic particle particle grain size scope is 1～12mm.
The preparation method of above-mentioned organic phase change material composite light-weight sintering ceramic particle, that adopt is the vacuum suck preparation method, its step is as follows: in vacuum reaction still or other container, light-weight sintering ceramic particle, organic phase change material and fire retardant are mixed by mass ratio 1: 0.5～5: 0.1～0.5 under 50～180 ℃ temperature; Slowly open the venting valve, reduce the interior vacuum tightness of reactor to normal pressure, the organic phase change material and the complete adsorption and permeation of fire retardant that dissolving also evenly are wrapped in the light-weight sintering ceramic particle particle surface enter light-weight sintering ceramic particle granule interior hole; Cooling, discharging has promptly obtained organic phase change material composite light-weight sintering ceramic particle particle.
Therefore, the present invention has following beneficial effect:
1. organic phase change material and fire retardant have penetrated into light-weight sintering ceramic particle granule interior hole fully, thereby solved organic phase change material and common building material bonded key technical problem, eliminated the influence of organic phase change material building material machinery performance and fire resistance.
2. the whole process of organic phase change material circulating phase-change all betides in the light-weight sintering ceramic particle granule interior hole, has thoroughly solved the cycle operation stability and the impermeable stability of phase-change accumulation energy aggregate.
3. made full use of the characteristics of light unit weight of light-weight sintering ceramic particle particle and big internal void, realized higher organic phase change material incorporation, guaranteed that this New-type phase change energy storage aggregate has high phase-change accumulation energy thermal capacitance.
4. preparation technology is simple, and easy to implement and control is beneficial to industrialization promotion and uses.
Embodiment
The present invention is further illustrated below by embodiment.
Embodiment 1: in the vacuum reaction still, be that sintered type light-weight sintering ceramic particle, the fusing point of 1～4mm is that polyoxyethylene glycol organic phase change material and ammonium phosphate fire retardant about 20 ℃ mixes by mass ratio under 50～60 ℃ temperature at 1: 5: 0.5 with particle size range; Slowly open the venting valve, reduce the interior vacuum tightness of reactor to normal pressure, the polyoxyethylene glycol and the fire retardant adsorption and permeation that dissolving also evenly are wrapped in the light-weight sintering ceramic particle particle surface enter light-weight sintering ceramic particle granule interior hole; Cooling, discharging has promptly obtained transformation temperature and is the organic phase change material composite light-weight sintering ceramic particle about 20 ℃.Promptly can be used for building operation in the haydite adding concrete with gained, add 10～40 kilograms of haydites in general per hundred kilograms of concrete.
By to the painted in advance of polyoxyethylene glycol and adopt opticmicroscope that the test analysis of organic phase change material composite light-weight sintering ceramic particle particle section situation is shown that polyoxyethylene glycol and fire retardant have penetrated into light-weight sintering ceramic particle granule interior hole fully.This organic phase change material composite light-weight sintering ceramic particle particulate material surface is hydrophilic substantially, dieseling can not occur in the flame, is heating repeatedly under 2000 round-robin situations of cooling simultaneously, the situation of polyoxyethylene glycol and fire retardant seepage and decomposition can not occur.After adding haydite of the present invention, made wallboard can reduce about 6 ℃ of fluctuations in indoor temperature, and energy-saving effect is remarkable.
Embodiment 2
In the vacuum reaction still, be that burning free type light-weight sintering ceramic particle, the fusing point of 5～12mm is that lipid acid organic phase change material and fire retardant about 30 ℃ mixes by mass ratio under 100～110 ℃ temperature at 1: 2: 0.2 with particle size range; Slowly open the venting valve, reduce the interior vacuum tightness of reactor to normal pressure, the lipid acid and the fire retardant adsorption and permeation that dissolving also evenly are wrapped in the light-weight sintering ceramic particle particle surface enter light-weight sintering ceramic particle granule interior hole; Cooling, discharging has promptly obtained transformation temperature and is the organic phase change material composite light-weight sintering ceramic particle particle about 30 ℃.
By to the painted in advance of lipid acid and adopt opticmicroscope that the test analysis of organic phase change material composite light-weight sintering ceramic particle particle section situation is shown that lipid acid and fire retardant have penetrated into light-weight sintering ceramic particle granule interior hole fully.This organic phase change material composite light-weight sintering ceramic particle particulate material surface is hydrophilic substantially, dieseling can not occur in the flame, is heating repeatedly under 2000 round-robin situations of cooling simultaneously, the situation of lipid acid seepage and decomposition can not occur.
Embodiment 3
In the vacuum reaction still, be that burning free type light-weight sintering ceramic particle, fusing point about 8～10mm is that paraffin organic phase change material and fire retardant about 35 ℃ mixes by mass ratio under 140 ℃ temperature at 1: 0.5: 0.1 with particle diameter; Slowly open the venting valve, reduce the interior vacuum tightness of reactor to normal pressure, the paraffin and the fire retardant adsorption and permeation that dissolving also evenly are wrapped in the light-weight sintering ceramic particle particle surface enter light-weight sintering ceramic particle granule interior hole; Cooling, discharging has promptly obtained transformation temperature and is the organic phase change material composite light-weight sintering ceramic particle particle about 35 ℃.
By to the painted in advance of paraffin and adopt opticmicroscope that the test analysis of organic phase change material composite light-weight sintering ceramic particle particle section situation is shown that paraffin and fire retardant have penetrated into light-weight sintering ceramic particle granule interior hole fully.This organic phase change material composite light-weight sintering ceramic particle particulate material surface is hydrophilic substantially, dieseling can not occur in the flame, is heating repeatedly under 2000 round-robin situations of cooling simultaneously, the situation of paraffin seepage and decomposition can not occur.
Claims (6)
1, a kind of organic phase change material composite light-weight sintering ceramic particle, it is characterized in that it is made up of light ceramic, organic phase change material and fire retardant, this three's mass ratio is 1: 0.5～5: 0.1～0.5, and described organic phase change material and fire retardant are in the light-weight sintering ceramic particle.
2, organic phase change material composite light-weight sintering ceramic particle according to claim 1 is characterized in that described fire retardant is one or more in ammonium phosphate, phosphoric acid or the Halogen alkane.
3, organic phase change material composite light-weight sintering ceramic particle according to claim 1 is characterized in that described organic phase change material is one or more in polyoxyethylene glycol, lipid acid, paraffin or the paraffin derivative of fusing point between 15～40 ℃.
4,, it is characterized in that described light-weight sintering ceramic particle particle grain size scope is 1～12mm according to claim 1 or 2 or 3 described organic phase change material composite light-weight sintering ceramic particles.
5, the described organic phase change material composite light-weight sintering ceramic particle of a kind of manufacturing claim 1 method is characterized in that it may further comprise the steps:
A: under the low pressure condition, light-weight sintering ceramic particle, organic phase change material and fire retardant are mixed by mass ratio 1: 0.5～5: 0.1～0.5 under 50～180 ℃ temperature;
B: system is risen to normal pressure, and the organic phase change material and the complete adsorption and permeation of fire retardant that dissolving also evenly are wrapped in the light-weight sintering ceramic particle surface enter light-weight sintering ceramic particle granule interior hole;
C: cooling, discharging has promptly obtained the organic phase change material composite light-weight sintering ceramic particle.
6, manufacturing organic phase change material composite light-weight sintering ceramic particle method according to claim 5 is characterized in that described low pressure condition is that pressure is less than 0.05Mpa.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531550A (en) * | 2011-12-22 | 2012-07-04 | 山东大学 | Poly fatty acid shape-stabilized phase change material and preparation method thereof |
| CN103524094A (en) * | 2013-09-17 | 2014-01-22 | 广东联塑科技实业有限公司 | Grass and tree fiber energy-storage calcium silicate board and preparation method thereof |
| CN104357018A (en) * | 2014-10-10 | 2015-02-18 | 中关村人居环境工程与材料研究院 | Environment-friendly composite phase change material and phase change energy storage device |
| CN110950564A (en) * | 2019-12-16 | 2020-04-03 | 长安大学 | Phase change aggregate for self-sensing and self-cooling of asphalt pavement and preparation method thereof |
| CN111171793A (en) * | 2020-01-06 | 2020-05-19 | 西安建筑科技大学 | Inorganic heat-storage unfired ceramsite and preparation method thereof |
| CN114231254A (en) * | 2021-12-14 | 2022-03-25 | 佛山欧神诺陶瓷有限公司 | Composite ceramic material with phase change temperature regulation function and preparation method and application thereof |
-
2006
- 2006-06-28 CN CNA2006100521610A patent/CN101096297A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531550A (en) * | 2011-12-22 | 2012-07-04 | 山东大学 | Poly fatty acid shape-stabilized phase change material and preparation method thereof |
| CN103524094A (en) * | 2013-09-17 | 2014-01-22 | 广东联塑科技实业有限公司 | Grass and tree fiber energy-storage calcium silicate board and preparation method thereof |
| CN104357018A (en) * | 2014-10-10 | 2015-02-18 | 中关村人居环境工程与材料研究院 | Environment-friendly composite phase change material and phase change energy storage device |
| CN104357018B (en) * | 2014-10-10 | 2017-11-24 | 中关村人居环境工程与材料研究院 | A kind of environmentally friendly phase change energy storage apparatus |
| CN110950564A (en) * | 2019-12-16 | 2020-04-03 | 长安大学 | Phase change aggregate for self-sensing and self-cooling of asphalt pavement and preparation method thereof |
| CN110950564B (en) * | 2019-12-16 | 2022-04-15 | 长安大学 | Phase change aggregate for self-sensing and self-cooling of asphalt pavement and preparation method thereof |
| CN111171793A (en) * | 2020-01-06 | 2020-05-19 | 西安建筑科技大学 | Inorganic heat-storage unfired ceramsite and preparation method thereof |
| CN111171793B (en) * | 2020-01-06 | 2021-10-15 | 西安建筑科技大学 | Inorganic heat-storage unfired ceramsite and preparation method thereof |
| CN114231254A (en) * | 2021-12-14 | 2022-03-25 | 佛山欧神诺陶瓷有限公司 | Composite ceramic material with phase change temperature regulation function and preparation method and application thereof |
| CN114231254B (en) * | 2021-12-14 | 2023-12-22 | 佛山欧神诺陶瓷有限公司 | Composite ceramic material with phase-change temperature regulation and preparation method and application thereof |
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