Research on microcapsules of phase change materials

Microcapsule technology is a kind of technology wrapping the solid or liquid into minute-sized particles within the field of micrometer or millimeter with film forming materials. This thesis introduces microcapsule technology of phase change materials and its main functions and the structural composition, preparation methods and characterization technology of microcapsule of phase change materials. The microcapsule of phase change materials is small in size and its temperature remains unchanged during the process of heat absorption and heat release. It is of great value in research and application prospect due to these characteristics.

Preparation and Properties of Paraffin/PMMA Shape-stabilized Phase Change Material for Building Thermal Energy Storage

The composite phase change material(PCM) consisting of phase change paraffin(PCP) and polymethyl methacrylate(PMMA) was prepared as a novel type of shape-stabilized PCM for building energy conservation through the method of bulk polymerization. The chemical structure, morphology, phase change temperature and enthalpy, and mechanical properties of the composite PCM were studied to evaluate the encapsulation effect of PMMA on PCP and determine the optimal composition proportion. FTIR and SEM results revealed that PCP was physically immobilized in the PMMA so that its leakage from the composite was prevented. Based on the thermo-physical and mechanical properties investigations, the optimal mass fraction of PCP in the composite was determined as 70%. The phase change temperature of the composite was close to that of PCP, and its latent heat was equivalent to the calculated value according to the mass fraction of PCP in the composite. For estimating the usability in practical engineering, thermal stability, reliability and temperature regulation performance of the composite were also researched by TG analysis, thermal cycling treatments and heating-cooling test. The results indicated that PCP/PMMA composite PCM behaved good thermal stability depending on the PMMA protection and its latent heat degraded little after 500 thermal cycling. Temperature regulation performance of the composite before and after thermal cycling was both noticeable due to its latent heat absorption and release in the temperature variation processes. The PCP/PMMA phase change plate was fabricated and applied as thermal insulator in miniature concrete box to estimate its temperature regulation effect under the simulated environmental condition. It can be concluded that this kind of PCP/PMMA shape-stabilized PCM with the advantages of no leakage, suitable phase change temperature and enthalpy, good thermal stability and reliability, and effective temperature regulation performance have much potential for thermal energy storage in building energy conservation.

Direct incorporation of paraffin wax as phase change material into mass concrete for temperature control: mechanical and thermal properties

Taking advantage of heat absorbing and releasing capability of phase change material(PCM),Paraffin wax-based concrete was prepared to assess its automatic temperature control performance.The mechanical properties of PCM concrete with eight different Paraffin wax contents were tested by the cube compression test and four-point bending test.The more Paraffin wax incorporated,the greater loss of the compressive strength and bending strength.Based on the mechanical results,four contents of Paraffin wax were chosen for studying PCM concrete's thermal properties,including thermal conductivity,thermal diffusivity,specific heat capacity,thermal expansion coefficient and adiabatic temperature rise.When the Paraffin wax content increases from 10%to 20%,the thermal conductivity and the thermal diffusivity decrease from 7.31 kJ/(m·h·°C)to 7.10 kJ/(m·h·°C)and from 3.03×10−3 m2/h to 2.44×10−3 m2/h,respectively.Meanwhile the specific heat capacity and thermal expansion coefficient rise from 5.38×10−1 kJ/(kg·°C)to 5.76×10−1 kJ/(kg·°C)and from 9.63×10−6/°C to 14.02×10−6/°C,respectively.The adiabatic temperature rise is found to decrease with an increasing Paraffin wax content.Considering both the mechanical and thermal properties,15%of Paraffin wax was elected for the mass concrete model test,and the model test results confirm the effect of Paraffin wax in automatic mass concrete temperature control.

Experimental design of paraffin/methylated melamine-formaldehyde microencapsulated composite phase change material and the application in battery thermal management system

In order to maintain the optimal operating temperature of the battery surface and meet the demand for thermal storage technology,battery thermal management system based on phase change materials has attracted increasing interest.In this work,a kind of core-shell structured microcapsule was synthesized by an in-situ polymerization,where paraffin was used as the core,while methanol was applied to mod-ify the melamine-formaldehyde shell to reduce toxicity and improve thermal stability.Moreover,three different types of heat conductive fillers with the same content of 10 wt.%,i.e.,nano-Al_(2)O_(3),nano-ZnO and carbon nanotubes were added,generating composites.The microcapsules were uniform,and were not affected by the thermal fillers,which were evenly dispersed around.The composite sample with carbon nanotubes(10 wt.%)showed the highest thermal conductivity of 0.50 W/(m K)and latent heat of 139.64 J/g.Furthermore,according to the leakage testing and battery charge/discharge experiments,compared with Al_(2)O_(3)and ZnO,the addition of carbon nanotubes remarkably enhances the heat storage ability as latent heat from 126.98 J/g for the prepared sample with Al_(2)O_(3)and 125.86 J/g for the one with ZnO,then to 139.64 J/g,as well as dissipation performance as a cooling effect by decreasing the sur-face temperature of battery from 2%to 12%of microcapsule,composite sample with carbon nanotubes presents a broad application prospect in battery thermal management system and energy storage field.

Photothermal phase change material microcapsules via cellulose nanocrystal and graphene oxide co-stabilized Pickering emulsion for solar and thermal energy storage

Phase change materials(PCMs)have attracted significant attention in thermal management due to their ability to store and release large amounts of heat during phase transitions.However,their widespread application is restricted by leakage issues.Encapsulating PCMs within polymeric microcapsules is a promising strategy to prevent leakage and increase heat transfer area with matrices.Moreover,photothermal PCM microcapsules are particularly desirable for solar energy storage.Herein,we fabricated photothermal PCM microcapsules with melamine-formaldehyde resin(MF)as shell using cellulose nanocrystal(CNC)and graphene oxide(GO)co-stabilized Pickering emulsion droplets as templates.CNC displays outstanding Pickering emulsifying ability and can facilitate the fixation of GO at the oil-water interface,resulting in a stable CNC/GO co-stabilized PCM Pickering emulsion.A polydopamine(PDA)layer was coated in-situ on the emulsion droplets via oxidization self-polymerization of dopamine.Meanwhile,GO was reduced to reduced GO(rGO)due to the reducing ability of PDA.The outmost MF shell of the PCM microcapsules was formed in-situ through the polymerization and crosslinking of MF prepolymer.The resulted PCM@CNC/rGO/PDA/MF microcapsules exhibit uniform sizes in the micrometer range,excellent leakage-proof performance,high phase change enthalpy(175.4 J g^(−1))and PCM encapsulation content(84.2%).Moreover,the presence of rGO and PDA endows PCM@CNC/rGO/PDA/MF microcapsules with outstanding photothermal conversion performance.The temperature of PCM@CNC/rGO/PDA/MF microcapsule slurries(15wt.%)can reach 73°C after light irradiation at 1 W cm^(−2).Therefore,photothermal PCM@CNC/rGO/PDA/MF microcapsules are promising for solar energy harvesting,thermal energy storage,and release in various applications,such as energy-efficient buildings and smart textiles.

Preparation and hygrothermal performance of composite phase change material wallboard with humidity control based on expanded perlite/diatomite/paraffin

Phase change material(PCM)can reduce the indoor temperature fluctuation and humidity control material can adjust relative humidity used in buildings.In this study,a kind of composite phase change material particles(CPCMPs)were prepared by vacuum impregnation method with expanded perlite(EP)as supporting material and paraffin as phase change material.Thus,a PCM plate was fabricated by mould pressing method with CPCMPs and then composite phase change humidity control wallboard(CPCHCW)was prepared by spraying the diatom mud on the surface of PCM plate.The composition,thermophysical properties and microstructure were characterized using X-ray diffraction instrument(XRD),differential scanning calorimeter(DSC)and scanning electron microscope(SEM).Additionally,the hygrothermal performance of CPCHCW was characterized by temperature and humidity collaborative test.The results can be summarized as follows:(1)CPCMPs have suitable phase change parameters with melting/freezing point of 18.23°C/29.42°C and higher latent heat of 54.66 J/g/55.63 J/g;(2)the diatom mud can control the humidity of confined space with a certain volume;(3)the combination of diatom mud and PCM plate in CPCHCW can effectively adjust the indoor temperature and humidity.The above conclusions indicate the potential of CPCHCW in the application of building energy efficiency.

Preparation of Paraffin/γ-Al2O3 Composites as Phase Change Energy Storage Materials

Paraffin/γ-Al2O3 composites as phase change energy storage materials were prepared by absorbing paraffin in porous network of γ-Al2O3.In the composite materials,paraffin was used as a phase change material(PCM)for thermal energy storage,and γ-Al2O3 acted as supporting materials.Characterizations were conducted to evaluate the energy storage performance of the composites,and differential scanning calorimeter results showed that the PCM-3 composite has melting latent heat of 112.9 kJ/kg with a melting temperature of 62.9 ℃.Due to strong capillary force and surface tension between paraffin and γ-Al2O3,the leakage of melted paraffin from the composites can be effectively prevented.Therefore,the paraffin/γ-Al2O3 composites have a good thermal stability and can be used repeatedly.

Experimental study and assessment of thermal energy storage mortar with paraffin/recycled brick powder composite phase change materials

Thermal energy storage recycled powder mortar(TESRM)was developed in this study by incorporating paraffin/recycled brick powder(paraffin/BP)composite phase change materials(PCM).Fourier transform infrared and thermogravimetric analysis results showed that paraffin/BP composite PCM had good chemical and thermal stability.The onset melting temperature and latent heat of the composite PCM were 46.49°C and 30.1 J·g−1.The fresh mortar properties and hardened properties were also investigated in this study.Paraffin/BP composite PCM with replacement ratio of 0%,10%,20%,and 30%by weight of cement were studied.The results showed that the static and dynamic yield stresses of TESRM were 699.4%and 172.9%higher than those of normal mortar,respectively.The addition of paraffin/BP composite PCM had a positive impact on the mechanical properties of mortar at later ages,and could also reduce the dry shrinkage of mortar.The dry shrinkage of TESRM had a maximum reduction about 26.15%at 120 d.The thermal properties of TESRM were better than those of normal mortar.The thermal conductivity of TESRM was 36.3%less than that of normal mortar and the heating test results showed that TESRM had good thermal energy storage performance.

Emerging low-density polyethylene/paraffin wax/aluminum composite as a form-stable phase change thermal interface material

Thermal interface materials(TIMs) play a vital role in the thermal management of electronic devices and can significantly reduce thermal contact resistance(TCR). The TCR between the solid–liquid contact surface is much smaller than that of the solid–solid contact surface, but conventional solid–liquid phase change materials are likely to cause serious leakage. Therefore, this work has prepared a new formstable phase change thermal interface material. Through the melt blending of paraffin wax(PW) and low-density polyethylene(LDPE), the stability is improved and it has an excellent coating effect on PW. The addition of aluminum(Al) powder improves the low thermal conductivity of PW/LDPE, and the addition of 15wt% Al powder improves the thermal conductivity of the internal structure of the matrix by 67%. In addition, the influence of the addition of Al powder on the internal structure, thermal properties, and phase change behavior of the PW/LDPE matrix was systematically studied. The results confirmed that the addition of Al powder improved the thermal conductivity of the material without a significant impact on other properties, and the thermal conductivity increased with the increase of Al addition. Therefore, morphologically stable PW/LDPE/Al is an important development direction for TIMs.

Preparation and Characterization of High-Temperature Non-Flowing Diurea/Paraffin/Oil Composites as Form-Stable Phase Change Materials

A series of form-stable phase change materials （FSPCMs） comprising paraffin as the latent heat storage material, diurea as the supporting material and base oil as the performance improvement agent were prepared. The diurea was synthesized in the system of paraffin/oil directly. A series of characterization was carried out for a deep understand- ing of shape stability and material properties of diurea-FSPCMs. The results showed that paraffin and base oil were packaged in the three-dimensional supra-molecular structures network which was formed by diurea. The dropping point of the prepared FSPCMs could reach 256 ℃ and the oil separation rate was as low as 1.19% at 100 ℃ for 30 h. The results of thermal properties tests showed that the prepared FSPCMs exhibited excellent thermal stability and the FSPCMs remained solid-like state in the temperature range from 25 to 200 ℃. This study proposes a novel method to prepare high-temperature non-flowing FSPCMs composites and methods to detect the thermal stability and shape stability of FSPCMs, which is helpful in understanding the shape stability mechanism and broadening the potential application of FSPCMs.

Study on the Heat Conduction of Phase-Change Material Microcapsules

The 3ω approach was used to measure the effective thermal conductivity of phase-change material microcapsules (PCMMs) based on urea formaldehyde and sliced paraffin. The effective thermal conductivities of PCMMs with different densities were measured within the phase-change temperature range. The relationships between effective thermal conductivity, density and temperature were analysed. The effective thermal conductivity reached peak values within the phase-change temperature range and the temperature peak value was consistent with the peak value of the phase-change temperature. The effective thermal conductivity increased with increasing density due to the decreased porosity of samples and their increased solid-phase conduction.

Preparation of Microcapsules Containing Erythritol with Interfacial Polycondensation Reaction by Using the (W/O) Emulsion

It was tried to microencapsulate erythritol as a phase change material with the interfacial polycondensation reaction method by using the (W/O) emulsion and to characterize the microcapsules prepared. In the experiment, toluene diisocyanate, diphenyl methane diisocyanate and hexamethylenediisocyanate were used to form the polyurethane shell and the effects of them on the heat storage density and the microencapsulation efficiency were investigated. Furthermore, the effect of supercooling prevention agent on the phase change behavior of erythritol was investigated. The microcapsules prepared with toluendiisocyanate monomer showed the highest heat storage density and the higher microencapsulation efficiency. Considerable supercooling phenomenon in the microcapsule was observed and prevented to a certain degree by addition of potassium dihydrogen phosphate and calcium sulfate as the supercooling prevention agent.

Preparation and Characterization of Poly(melamine-urea-formaldehyde) Tetradecanol Microcapsules Coated with Silver Particles

A novel type of microencapsulated phase change materials(microPCMs)based on 1-tetradecanol(TD)core and silver-coated poly(melamine-urea-formaldehyde)(MUF)shell was successfully synthesized by in situ polymerization method followed by silver reduction.Fourier-transform infrared spectroscopy(FTIR),X-ray diffraction(XRD),scanning electron microscopy with energy dispersive X-ray spectrometry(SEM/EDS),thermogravimetric analysis(TGA)and differential scanning calorimetry(DSC)were used to characterize the chemical structure,morphology and thermal properties of the as-prepared silver-coated microPCMs.FTIR analysis confirmed the successful encapsulation of TD with MUF wall materials.The SEM and EDS results indicated that the prepared silver-coated MUF microPCMs exhibited uniform spherical shape with a perfect silver outer layer.From XRD analysis,the Ag metal dispersed on the surface of microcapsules presented the form of elementary substance.The deposition weight of silver particles on the microcapsule surface increased with increasing the amount of silver nitrate,as indicated by EDS tests.The DSC results indicated that the melting temperature and the melting latent heat of microPCMs modified with 0.7g of silver nitrate in 150mL aqueous solution were 39.2°C and 126.6J·g^-1,respectively.Supercooling of the microPCMs coated with silver particles was effectively suppressed,compared with that of microPCMs without Ag.Thus,the encapsulation of TD with silver-coated MUF shell developed by this work can be an effective method to prepare the microPCMs with enhanced thermal transfer performance and phase change properties.

Preparation and characterization of silica microcapsules containing butyl-stearate via sol-gel method

For thermal energy storage application in energy-saving building materials,silica microcapsules containing phase change material were prepared using sol-gel method in O/W emulsion system. In the system droplets in microns are formed by emulsifying an organic phase consisting of butyl-stearate as core material. The silica shell was formed via hydrolysis and condensation from tetraethyl silicate with acetate as catalyst. The SEM photographs show the particles possess spherical morphology and core-shell structure. The as-prepared silica microcapsules mainly consist of microsphere in the diameter of 3-7 μm and the median diameter of these microcapsules equals to 5.2 μm. The differential scanning calorimetry(DSC) curves indicate that the latent heat and the melting point of microcapsules are 86 J/g and 22.6 ℃,respectively. The results of DSC and TG further testify the microcapsules with core-shell structure.

Multifunctional HDPE/CNTs/PW composite phase change materials with excellent thermal and electrical conductivities

The risk of leakage and low thermal conductivity severely hinder the wide application of phase change materials(PCMs).In this work,the high-density polyethylene/carbon nanotubes(HDPE/CNTs)porous scaffolds were successfully fabricated via a sacrificial template method followed by the general melt blending and water solvent etching.Subsequently,a series of paraffin wax HDPE/CNTs/PW composite PCMs were obtained combined with the simple vacuum impregnation method.The obtained HDPE/CNTs porous scaffolds can effectively avoid the leakage of PW,meanwhile,the thermal conductivity and electrical conductivity of HDPE/CNTs/PW-3:7 are increased by 2.94 times and 13 orders of magnitude compared with the HDPE/PW-3:7 respectively,also,it exhibits high phase change enthalpy(153.95 J/g for melting enthalpy and 152.82 J/g for crystallization enthalpy).From the above perspectives,the HDPE/CNTs/PW-3:7 has promising potential value in the application of light-to-thermal conversion,electro-to-thermal conversion and thermal energy storage.

Preparation and characterization of magnetic phase-change microcapsules

Magnetic microcapsules containing paraffin cores within urea-formaldehyde shells were fabricated utilizing in situ polymerization, with iron nano-particles as magnetic particles. The thermal properties, surface morphologies, magnetic properties and iron nano-particles content of the magnetic phasechange microcapsules were investigated by scanning electronic microscopy (SEM), differential scan- ning calorimetry (DSC), vibrating sample magnetometry (VSM) and inductively coupled plasma quantometry (ICP). The influence of iron nano-particles on morphologies was also considered. The results indicate that the melting point of magnetic phase-change microcapsules is almost identical to that of paraffin. The magnetism parameters such as specific saturation magnetization and residual magnetization of magnetic phase-change microcapsules increase with the increase of iron nano-particles content.

Enhanced photothermal conversion and thermal conductivity of phase change n-octadecane microcapsules shelled with nano-SiC doped crosslinked polystyrene

Microcapsules incorporating phase change material n-octadecane(ODE)shelled with crosslinked polystyrene(CLPS)were prepared via the suspension polymerization.SiC nanoparticles(nano-SiC)were employed to modify the shell to improve the heat transfer and photothermal conversion of the microcapsules.The scanning electron microscopic analysis revealed the microcapsules of a general spherical shape.The surface components and chemical composition of the microcapsule samples were evaluated by the energy-dispersive X-ray and Fourier transform infrared spectroscopy,confirming that the nano-SiC have been embedded in the CLPS shell.Results show that the microcapsule sample with 1.25 wt.%nano-SiC(denoted as MPCM3)exhibits the best heat property among the four kinds of samples prepared with various nano-SiC dosages,and all the nano-SiC doped samples have improved thermal conductivity and photothermal conversion as compared to the microcapsule sample without doping(denoted as MPCM1).Compared to the MPCM1,the thermal conductivity of the MPCM3 is increased by 65.3%,reaching 0.124±0.005 W·m^(−1)·K^(−1).The MPCM3 has excellent thermal stability as well.Differential scan-ning calorimetry examination shows that the MPCM3 has higher melting and crystallization enthalpies than the MPCM1,achieving 106.8±0.3 J·g^(−1) and 104.9±0.2 J·g^(−1),respectively.In the photothermal conversion experi-ments,the MPCM3 exhibited great photothermal conversion capability,with a 54.91%photothermal conversion efficiency,which is 145.68%higher than that of the MPCM1.

Preparation of Palygorskite-based Phase Change Composites for Thermal Energy Storage and Their Applications in Trombe Walls

Palygorskite/paraffin phase-change composites were prepared by the combination of purified palygorskite clay and sliced paraffin. Then, this composite was used in the Trombe wall to improve its energy storage ability. Further, its energy storage ability was compared to that of ordinary concrete wall through contrastive test. The experiments show that palygorskite clay is a type of clay mineral with strong adsorption ability, and the purity of natural palygorskite clay can reach up to 97.1% after certain purification processes. Paraffin is well adsorbed by palygorskite, and the test results show that the optimal adsorption ratio is palygorskite： paraffin = 2：1（mass ratio）. Palygorskite/paraffin phase change composites can be obtained by using palygorskite as the adsorbing medium to adsorb paraffin. The composite materials exhibit good heat storage（release） performance, which can store heat with increasing environment temperature and release heat with decreasing temperature. This property not only increases the inertia to environment temperature change, but also promotes the energy migration in different time and space, thus achieving a certain energy-saving effect. The application of palygorskite/paraffin phase change composite materials to the Trombe wall can significantly reduce the fluctuation of indoor temperature and enhance the thermal inertia of indoor environment. From the aspect of energy storage effect, the Trombe wall fabricated using PCMs is significantly superior to the concrete wall with the same thickness.

由石蜡基相变材料和煤渣改良的粉砂土的冻融性能

【目的】针对季节冻土区渠道的衬砌结构因冻融作用而受损的现状,同时为了解决石蜡基相变材料(phase change materials, PCM)的泄露,并满足煤渣的再利用需求,研究石蜡基PCM和煤渣对土体冻融性能的影响。【方法】以粉砂土为研究对象,选取石蜡基PCM和煤渣作为改良剂,制备石蜡基PCM改良土和石蜡基PCM-煤渣改良土;通过冻融循环作用下的体积变化率试验、无侧限抗压强度试验,微观结构及潜热研究土体的体积和无侧限抗压强度的变化。【结果】石蜡基PCM能抑制粉砂土的冻融变形,质量分数为8%时2种改良土的体积变化率最小;随着冻融循环次数的增加,土体的无侧限抗压强度均降低,降低速率先大后小;循环次数相同时,加入煤渣的改良土的无侧限抗压强度均大于未加入煤渣的;冻融循环9次后,石蜡基PCM质量分数为10%的石蜡基PCM改良土的无侧限抗压强度最低;2种改良土的结构比粉砂土更密实、稳定;潜热的吸收或释放延缓了土体冻融过程。【结论】将石蜡基PCM和煤渣共同掺入粉砂土,能控制土体的冻融变形且效果稳定,改善土体的冻融性能,减轻季节冻土区输水渠道衬砌结构的冻害,提高煤渣的利用率。

不同温度条件下相变石蜡力学性能分析

对3种不同相变温度的石蜡材料(PCM-28、PCM-18和PCM-10)在不同温度下的基本力学性能参数进行了系统的压缩实验,计算出对应的弹性模量和泊松比。结果表明:PCM-18和PCM-10的抗压强度随温度的降低而有所提高,但PCM-28的抗压强度随温度的降低反而呈现出下降趋势。在单轴压缩条件下PCM-28和PCM-18的应力-应变曲线主要经历了压实阶段、弹性变形阶段、裂纹扩展阶段和裂纹后破坏阶段4个明显阶段,最终表现为脆性破坏。PCM-10在经历压实阶段和弹性变形阶段后进入塑性阶段,曲线发展近似水平,且整个过程无明显裂纹出现。