Photocrosslinked biobased phase change material for thermal energy storage

A series of novel photocrosslinked biobased shape‐stabilized phase change materials (PCMs) based on octadecanol, eicosanol and docosanol have been prepared by UV technique for the purpose of thermal energy storage applications. Epoxidized soybean oil was reacted with acrylic acid to form acrylated soybean oil (ASO). The structure and composition, cross‐section morphology, thermal stability performances and phase change behaviors of ASO and UV‐cured PCMs were examined by using Attenuated total reflection fourier transform infrared spectroscopy, thermogravimetric analysis system (TGA), scanning electron microscopy, and differential scanning calorimetry. The results indicate that the UV‐cured biobased PCMs possess perfect phase change properties and a suitable working temperature range. The heating process phase change enthalpy is measured between 30 and 68 J/g, and the freezing process phase change enthalpy is found between 18 and 70 J/g. The decomposition of UV‐cured PCMs started at 260 °C and reached a maximum of 430 °C. All the biobased UV‐cured PCMs improved latent heat storage capacity in comparison with the pristine ASO sample. With the obtained results we conclude that, these materials promise a great potential in thermal energy storage applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43757.     

Synthesis and thermal properties of poly(acrylonitrile‐co‐allyl glycidyl ether)‐graft‐methoxypoly(ethylene glycol) copolymers as novel solid–solid phase‐change materials for thermal energy storage

We synthesized a series of poly(acrylonitrile‐co‐allyl glycidyl ether)‐graft‐methoxypoly(ethylene glycol) (PAA‐g‐MPEG) copolymers as novel polymeric solid–solid phase‐change materials by grafting methoxypoly(ethylene glycol) (MPEG) to the main chain of poly(acrylonitrile‐co‐allyl glycidyl ether) (PAA). PAA was the skeleton, and MPEG was a functional side chain, which stored and released heat during its phase‐transition process. Fourier transform infrared spectroscopy and ¹H‐NMR spectroscopy analysis were performed to investigate the chemical structures. The crystalline morphology and crystal structures were also measured with polarized optical microscopy and X‐ray diffraction. Moreover, the thermal‐energy‐storage properties, thermal stability, and thermal reliability of the PAA‐g‐MPEG copolymers were characterized by differential scanning calorimetry and thermogravimetric analysis (TGA) methods. These analysis results indicate that the MPEG chains were successfully grafted onto PAA, and we found that the PAA‐g‐MPEG copolymers had typical solid–solid phase‐transition temperatures in the range 11–54 °C and high latent heat enthalpies between 44 and 85 J/g. In addition, the as‐prepared PAA‐g‐MPEG copolymers showed reusability and thermal reliability, as shown by the thermal cycle testing and TGA curves. Therefore, the synthesized PAA‐g‐MPEG copolymers have considerable potential for thermal energy storage. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46641.     

Preparation and swelling properties of semi‐IPN hydrogels based on chitosan‐g‐poly(acrylic acid) and phosphorylated polyvinyl alcohol

The phosphorylated poly(vinyl alcohol) (P‐PVA) samples with various substitution degrees were prepared through the esterification reaction of PVA and phosphoric acid. By using chitosan (CTS), acrylic acid (AA) and P‐PVA as raw materials, ammonium persulphate (APS) as an initiator and N,N‐methylenebisacrylamide as a crosslinker, the CTS‐g‐PAA/P‐PVA semi‐interpenetrated polymer network (IPN) ssuperabsorbent hydrogel was prepared in aqueous solution by the graft copolymerization of CTS and AA and followed by an interpenetrating and crosslinking of P‐PVA chains. The hydrogel was characterized by Fourier transform infrared (FTIR), scanning electron microscopy (SEM), and differential scanning calorimetry (DSC) techniques, and the influence of reaction variables, such as the substitution degree and content of P‐PVA on water absorbency were also investigated. FTIR and DSC results confirmed that PAA had been grafted onto CTS backbone and revealed the existence of phase separation and the formation of semi‐IPN network structure. SEM observations indicate that the incorporation of P‐PVA induced highly porous structure, and P‐PVA was uniformly dispersed in the polymeric network. Swelling results showed that CTS‐g‐PAA/P‐PVA semi‐IPN superabsorbent hydrogel exhibited improved swelling capability (421 g·g^?1 in distilled water and 55 g·g^?1 in 0.9 wt % NaCl solution) and swelling rate compared with CTS‐g‐PAA/PVA hydrogel (301 g·g^?1 in distilled water and 47 g·g^?1 in 0.9 wt % NaCl solution) due to the phosphorylation of PVA. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Nucleating agent for poly(L‐lactic acid)—An optimization of chemical structure of hydrazide compound for advanced nucleation ability

A series of compounds having hydrazide groups was prepared and evaluated as nucleating agent for poly(L ‐lactic acid) by differential scanning calorimetry. Hydrazide compounds derived from benzoic acid, 2‐hydroxybenzoic acid, 3‐tert‐butylbenzoic acid, and 2‐aminobenzoic acid, where two of hydrazide compounds connected by four methylene chain were evaluated in series. Benzoylhydrazide type was found to be more effective on the enhancement of crystallization of poly(L ‐lactic acid). Effects of connecting length of methylene chain numbers between two of benzoylhydrazide on the nucleation ability were also evaluated. Benzoylhydrazide‐type compound having 10 methylenes, that is, decamethylenedicarboxylic dibenzoylhydrazide demonstrated excellent nucleation ability, and the resulted crystallization temperature and enthalpy of PLA with the compound of 1 wt % loading were 131°C and 46 J g^?1. The achieved crystallization temperature and enthalpy were over 10°C and over 10 J g^?1 higher than PLA with conventional nucleating agents, such as talc and ethylenebis (12‐hydroxystearylamide). Thus, the improvement in processability, productivity, and heat resistance of PLA is suggested to be achieved by using decamethylenedicarboxylic dibenzoylhydrazide as a nucleating agent. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 198–203, 2007     

Si@S-doped C anode with high cycling stability using PVA-g-PAA water soluble binder for lithium-ion batteries

The nanostructured Si@S-doped C (Si/C) hybrid is synthesized via a mild hydrothermal process of glucose and the simultaneous polymerization of 3,4-ethylenedioxythiophene and poly(sodium-4-styrene sulfonate) on the surface of nano-Si powders, then followed by a calcination process. A new water soluble polymer of poly(vinyl alcohol) (PVA) grafted with poly(acrylic acid) (PAA) is synthesized via a free-radical polymerization of acrylic acid (AA) in a 1:1 weight ratio in PVA water solution. The Si/C anode using PVA-g-PAA binder, exhibits improved lithium storage properties and cycling stability than that of the parallel electrode with carboxymethyl cellulose binder, which exhibits an initial coulombic efficiency (82.0%), even a reversible capacity of 487 mAh g⁻¹ after 300 cycles with 81.2% capacity retention at 0.4 A g⁻¹. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48764.     

Study by thermal analysis of composites prepared from silica gel,furfuryl alcohol and acetaldehyde

Composites from furfuryl alcohol, acetaldehyde and silica gel were prepared with trifluoracetic acid as a catalyst. The composites were studied by TGA and DSC. The TGA results showed three main losses of weight, the first of which was ascribed to water. The percentage of polymer in the composites reached a limit value, independently of the ratio of furfuryl alcohol/acetaldehyde used. The layer of polymer that covers the silica was not completely cross‐linked. The composites contain soluble oligomers with 97: M _n < 580 g mol^?1, that could be extracted with THF. The soluble fraction of composites prepared from mixtures of furfurylic alcohol and acetaldehyde decreased as the proportion of the acetaldehyde increased. The DSC of the samples indicated a T_g between ?8 and ?15 °C that disappeared after an extraction with THF. The DSC of the oligomers removed showed a possible T_g at 13 °C and an exothermic peak between 70 and 170 °C which corresponded to an enthalpy of 326.1 J g^?1. © 2003 Society of Chemical Industry     

聚丙烯蜡固-固相变材料的制备与工艺优化

针对聚丙烯蜡相变材料难以乳化分散、离子交联定型的问题,利用聚丙烯酸（PAA）羧基的亲水性,易离子化特性,设计了低聚合度聚丙烯酸（PAA）接枝聚丙烯蜡,以自乳化方法制备聚丙烯蜡乳液,通过常温离子交联,在水介质中、短周期内制备了聚丙烯蜡固-固相变材料（PPW SS-PCMs）。首先利用红外光谱仪、核磁共振波谱仪、扫描电子显微镜分析测试,探讨了丙烯酸的浓度及瞬时浓度对聚丙烯蜡（PPW）接枝产物自乳化能力的影响。然后,利用偏光显微镜、X射线衍射仪、差示扫描量热仪、热重分析仪对PPW接枝产物及PPW SS-PCMs的结晶性能、热稳定性做了测试和分析。结果表明：随着丙烯酸（AA）质量占比升高,定型相变材料的相变焓随AA含量的提升而下降。在一定范围内,通过提高AA瞬时浓度能提高改性PPW的自乳化能力,减少定型组分添加量。当AA、PPW、BPO质量比为0.36∶1∶0.05及滴加速率为9mL/min时,所制备的PPW SS-PCMs的结晶温度为52.46℃,结晶焓为-53.61J/g,储能效率为81.26%,具有较好的热稳定性。     

Poly(2‐alkyloyloxyethylacrylate) and poly(2‐alkyloyloxyethylacrylate‐co‐methylacrylate) comblike polymers as novel phase‐change materials for thermal energy storage

A series of poly(2‐alkyloyloxyethylacrylate) and poly(2‐alkyloyloxyethylacrylate‐co‐methylacrylate) polymers as novel polymeric phase‐change materials (PCMs) were synthesized starting from 2‐hydroxyethylacrylate and fatty acids. The chemical structure and crystalline morphology of the synthesized copolymers were characterized with Fourier transform infrared and ¹H‐NMR spectroscopy and polarized optical microscopy, respectively, and their thermal energy storage properties and thermal stability were investigated with differential scanning calorimetry and thermogravimetric analysis, respectively. The thermal conductivities of the PCMs were also measured with a thermal property analyzer. Moreover, thermal cycling testing showed that the copolymers had good thermal reliability and chemical stability after they were subjected to 1000 heating/cooling cycles. The synthesized poly(2‐alkyloyloxyethylacrylate) polymers and poly(2‐alkyloyloxyethylacrylate‐co‐methylacrylate) copolymers as novel PCMs have considerable potential for thermal energy storage and temperature‐control applications. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Proton conducting PAMPS networks: From flexible to rigid materials

To elaborate tailor‐made proton conducting materials showing an interesting range of flexibility, a series of conetworks combining poly(2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid) (PAMPS) and poly(ethylene oxide) dimethacrylate (PEGDM) with various chain lengths was synthesized. The homogeneity of these conetworks was checked by differential scanning calorimetry and dynamic mechanical thermal analysis. The swelling behavior of these materials is strongly influenced by the amount of sulfonic acid groups and the endothermal peak temperature, characteristic of the presence of bound water in the conetwork, increases from 65 to 120°C when AMPS amount increases from 10 to 75 wt %. In addition, the proton conductivity of these materials varies from 10^?3 to 10^?1 S cm^?1, depending on the AMPS amount. The storage moduli were found to be affected by both the AMPS content in the conetwork and its crosslinking density. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of slow‐release nitrogen fertilizer with water absorbency: Based on poly(acrylic acid‐acrylic amide)/Na‐bentonite

A novel slow‐release nitrogen fertilizer with high‐water absorbency (SRNFWA) was prepared by cross‐linking poly (acrylic acid‐acrylic amide)/bentonite and urea. The synthesis conditions were studied systematically and optimized by using the response surface methodology (RSM). Meanwhile, the effects of the concentration of cross‐linker, initiator, bentonite, and degree of neutralization of acrylic acid on WA were investigated. The SRNFWA was characterized by Fourier transform infrared (FTIR) spectroscopy, elemental analysis, and scanning electron microscopy (SEM). The results of SEM showed the undulant and coarse surface, facilitated the permeation of nutrition into the polymeric network. We also investigated the slow release property and release mechanism of the nitrogen from the network structure, and the WA in different external solutions. The released characteristic of nitrogen was less than 15% by the third day and reached up to almost 75% after 30 days in distilled water. The WA was 700 g g^?1 and 150 g g^?1 in distilled water and 0.9 wt % NaCl solutions, respectively. These studies exhibited the excellent slow‐release property and WA capacity of this polymer in 0.9 wt % NaCl solution and could be quite effective in improving the utilization of fertilizer and its water retention capacity simultaneously. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and characterization of PEG/MDI/PVA copolymer as solid–solid phase change heat storage material

In this article, a novel solid–solid phase change heat storage material was synthesized via a two‐step condensation reaction of high molecular weight poly(ethylene glycol) (PEG4000) with poly(vinyl alcohol) (PVA) and 4,4′‐diphenylmethane diisocyanate (MDI). To characterize the resulting product in comparison with pristine PEG4000, Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analyses, and polarization optical microscopy measurements were employed to investigate functionality, thermal properties, and crystalline behavior. The results indicated that the crosslinking phase change material showed typical solid–solid phase transition properties, and its phase change enthalpy reached 72.8 kJ/kg. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Phase change material with flexible crosslinking for thermal energy storage

The utilization of renewable energy through phase change materials (PCMs) is particularly attractive for the realization of sustainable society. Herein, a flexible but reliable solid–solid PCM was successfully synthesized by the integration of quadruple H-bonding crosslinks with polyethylene glycol (PEG)-based polyurethanes. The strong quadruple H-bonding from the dimerization of 2-ureido-4 [1H]-pyrimidinone (UPy) units could act as dynamic cross-links to maintain shape stability. PEG chains in flexible polymer network serve as phase change ingredients, affording thermal energy storage capacity. The physical crosslink density and phase change enthalpy can be adjusted. In contrast to chemical crosslinks, the physical crosslinks of UPy provide reprocessability of the prepared PCMs and show little hindrance on the crystallization of PEG chains. The chemical structure, phase transformation, crystallization, and thermal properties of prepared PCMs were characterized by fourier transform infrared spectroscopy, differential scanning calorimetry (DSC), X-ray diffraction, polarizing microscope, and thermogravimetric analysis. DSC analysis shows that the prepared PCM can store 101.9 J g⁻¹ when PCMs undergo phase change process. Moreover, the accelerated thermal cycling test and leakage test are also conducted to illustrate the thermal reliability and shape-stable properties. These PCMs that possess high phase change enthalpy and outstanding reprocessability are alternative for solar energy collection and waste heat recovery. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48497.     

Poly(polyethylene glycol methyl ether methacrylate) as novel solid-solid phase change material for thermal energy storage

Poly(polyethylene glycol methyl ether methacrylate) as novel solid–solid phase change materials (PCMs) for thermal energy storage was prepared via the facile bulk polymerization of polyethylene glycol methyl ether methacrylate and was characterized by Fourier transform infrared, ¹³C-NMR, X-ray diffraction, differential scanning calorimetry, and thermogravimetric analysis measurements. Based on the results, it is indicated that the poly (polyethylene glycol methyl ether methacrylate) as novel PCM showed solid–solid properties with suitable transition temperature, high transition enthalpy, and good thermal stability, which was apt to crystallize due to the flexibility of long polyether side chain. This novel PCMs have advantages for the potential application in energy storage. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Pure and complex nanostructures using poly[bis(triiso‐propylsilylethynyl) benzodithiophene‐bis(decyltetradecyl‐thien) naphthobisthiadiazole], carbon nanotubes and reduced graphene oxide for high‐performance polymer solar cells

Crystallization of poly[bis(triiso‐propylsilylethynyl) benzodithiophene‐bis(decyltetradecyl‐thien) naphthobisthiadiazole] (PBDT‐TIPS‐DTNT‐DT) was investigated in supramolecules based on carbon nanotubes (CNTs) and reduced graphene oxide (rGO) and their grafted derivatives. The principal peaks of PBDT‐TIPS‐DTNT‐DT crystals were in the range 3.50°–3.75°. By grafting the surface of the carbonic materials, the assembling of polymer chains decreased because of hindrance of poly(3‐dodecylthiophene) (PDDT) grafts against π‐stacking. The diameters of CNT/polymer and CNT‐g‐PDDT/polymer supramolecules were 160 and 100 nm. The rGO/polymer supramolecules had the highest melting point (T_m = 282 °C) and fusion enthalpy (ΔH_m = 25.98 J g^?1), reflecting the largest crystallites and the most ordered constituents. Nano‐hybrids based on grafted rGO (276 °C and 28.26 J g^?1), CNT (275 °C and 27.32 J g^?1) and grafted CNT (268 °C and 22.17 J g^?1) were also analyzed. T_m and ΔH_m values were significantly less in corresponding melt‐grown systems. The nanostructures were incorporated in active layers of PBDT‐TIPS‐DTNT‐DT:phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) solar cells to improve the photovoltaic features. The best results were detected for PBDT‐TIPS‐DTNT‐DT:PC₇₁BM:rGO/polymer systems having J_sc = 13.11 mA cm^?2, fill factor 60% and V_oc = 0.71 V with an efficacy of 5.58%. On grafting the rGO and CNT, efficiency reductions were 12.01% (5.58%–4.91%) and 9.34% (4.07%–3.69%), respectively. © 2019 Society of Chemical Industry     

Immobilization of β‐amylase using polyacrylamide polymer derivatives

Barley β‐amlyase was immobilized on two polymeric materials; poly(acrylamide–acrylic acid) resin [P(AM‐AAc)] and poly(acrylamide–acrylic acid–diallylamine–HCl) resin [P(P(AM‐AAc‐DAA‐HCl) using two different methods: covalent and cross‐linking immobilization. Thionyl chloride, used to activate the polymers for covalent immobilization, has the advantage that it is able to react with a number of surface groups of protein under very mild conditions. Cross‐linking with glutaraldehyde gave a higher coupling yield (approximately 70%) than covalent immobilization (approximately 20%). The activity and stability of the resulting biopolymers have been compared with those of free β‐amylase. The specific activity of the immobilized enzyme was significantly influenced by the amount of enzyme loaded onto the polymers, the optimal level being 3.5 mg g^?1 polymer. It was found that the immobilized β‐amylase stored at 4°C retained approximately 90% of its original activity after 30 days, whereas free β‐amylase stored in solution at 4°C retained only 47% of its activity after same period. The difference in long term stability was more significant when the enzyme was stored at room temperature; the immobilized enzyme maintained 40% of its activity after 30 days, whereas the residual activity of free enzyme was only 10%. Copyright © 2003 Society of Chemical Industry     

Graft copolymerization of acrylic acid onto xanthum gum using a potassium monopersulfate/Fe2+ redox pair

A previously unreported graft copolymer of xanthan gum (XOH) with acrylic acid was synthesized and the reaction conditions were optimized using a potassium monopersulfate (PMS)/Fe²⁺ redox pair. Grafting ratio, add on, and conversion increase with an increase in the ferrous ion concentration (2.0 × 10^?3 to 5.0 × 10^?3 mol dm^?3) and PMS concentration (1.0 × 10^?3 to 4.0 × 10^?3 mol dm^?3). It was observed that grafting takes place efficiently when the acrylic acid concentration and temperature were 5.0 × 10^?2 mol dm^?3 and 35°C, respectively. Samples of xanthan gum and xanthan gum–g–acrylic acid were subjected to thermogravimetric analysis with the objective of studying the effect of grafting of acrylic acid on the thermal stability of xanthan gum. The graft copolymer was found to be more thermally stable than xanthan gum. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1341–1346, 2003     

Encapsulation of polar phase change materials via multiemulsification and crosslinking method and its application in building

Phase change microcapsules are prepared using chitosan as shell material and aliphatic alcohol/aliphatic acid as core material via multiemulsification and crosslinking method. During the phase change process, the phase change microcapsules store and release heat energy. The enthalpy value of these phase change microcapsules is high enough to be used for application. Suitable phase change temperature can be obtained by changing the core material easily. The resulted microcapsules showed excellent thermal stability. Thermal gravity analysis results showed that the microcapsules remain stable below 200 °C. The microcapsules also exhibited good solvent resistance because of the crosslinking of the shell material chitosan. By integrating the microencapsulated phase change materials (2.5%) into building walls, the inner temperature of model house remained 2 °C higher than that without PCM during the test process. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47837.     

红外隐身用相变微胶囊材料的制备

以丙烯酸为囊壁材料,石蜡为囊芯,采用原位聚合法制备了相变微胶囊材料。利用SEM和FTIR表征了所制备相变微胶囊的形貌和化学结构。相变微胶囊的DSC测试表明,相变温度在37℃左右,相变潜热在144J/g左右,达到了红外隐身所要求的较高热焓值,并将其填充在可控加热的金属板内,红外成像图显示具有明显的降温功能。     

Synthesis and characterization of cassava starch graft poly(acrylic acid) and poly[(acrylic acid)‐co‐acrylamide] and polymer flocculants for wastewater treatment

Starch‐g‐poly(acrylic acid) and poly[(acrylic acid)‐co‐acrylamide] synthesized via chemically crosslinking polymerization were then each mixed with inorganic coagulants of aluminum sulfate hydrate [Al₂(SO₄)₃·18H₂O], calcium hydroxide [Ca(OH)₂], and ferric sulfate [Fe₂(SO₄)₃] in a proper ratio to form complex polymeric flocculants (CPFs). All CPFs exhibited low water absorbency than those of the uncomplexed superabsorbent copolymers. The color reduction by the CPFs was tested with both synthetic wastewater and selected wastewater samples from textile industries. The synthetic wastewater was prepared from a direct dye in a concentration of 50 mg dm^?3 at pH 7. The CPFs of poly[(acrylic acid)‐co‐acrylamide] with calcium hydroxide at a ratio of 1:2 is the most effective CPF for the wastewater color reduction. The CPF concentration of 500 mg dm^?3 could reduce the color of the synthetic wastewater containing the direct dye solution by 95.4% and that of the industrial wastewater by 76%. Starch‐g‐poly(acrylic acid)/Ca(OH)₂ CPF can reduce the synthetic direct dye and the industrial wastewater by 74% and 18%, respectively. Chemical oxygen demand, residual metal ion concentrations, pHs, turbidity of the wastewater were also investigated and the potential use of the complex polymer flocculants for textile wastewater treatment was indicated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2915–2928, 2006     

The role of radical polymerization in the production of thermoregulating microcapsules or polymers from saturated and unsaturated fatty acids

The microencapsulation of linoleic (LinA), oleic, erucic, and palmitic acids (PAs) from styrene and divinylbenzene were studied by using the suspension‐like polymerization technique. All materials exhibited a spherical shape, with a particle size between 166 and 416 μm. The phase change material (PCM) content decreased with the presence of double bonds in the fatty acid molecule. The thermal energy storage (TES) capacity of the microcapsules (MC) containing saturated PA was the highest (123.30 J g^?1). Whereas, the lowest TES capacity was observed for the LinA. TES capacity values from unsaturated fatty acid materials and the high particle yield indicated that these kinds of acids played two different roles, as PCM and also as monomers, in the radical polymerization processes. At high initiator concentrations, the unsaturated fatty acids were observed to react. This was confirmed by Fourier transform infrared where the peak assigned to the C?C bond disappears in the spectrum of MC. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45970.