TECHNICAL NOTE Channel forma tion and visualization of melting and crystallization behaviors in direct-conta ct latent heat storage systems Sven Kunkel 1 | Philipp Schütz 2 | Frederik Wunder 1 | Stefan Krimmel 2 | Jörg Worlitschek 2 | Jens-Uwe Repke 3 | Matthias Rädle 1 1 Center for Mass Spectrometry and Optical Spectroscopy, Hochschule Mannheim — University of Applied Sciences, Mannheim, Germany 2 Competence Centre for Thermal Energy Storage, Hochschule Luzern — University of Applied Sciences and Arts, Horw, Switzerland 3 Dynamics and Operation of Technical Systems, Technische Universität Berlin, Berlin, Germany Correspondence Frederik Wunder, Center for Mass Spectrometry and Optical Spectroscopy, Hochschule Mannh eim — University of Applied Sciences, Paul-Wittsack-Straße 10, Mannheim 68163, Germany. Email: f.wunder@hs-mannheim. de Summary Thermal storage syste ms are an essential component for incr easing the share of renewable ene rgies in reside ntial heatin g and for the valorization of waste heat. A key challenge for the widespread applicat ion of thermal storage systems is their limited power-to-capacity ratio. One potent ial solution for this challenge is repre- sented by direct-contact lat ent heat st orage systems, i n which a phase change material (PCM) is in direct contact with an immiscible heat transfer fluid (HTF). To demonstrate the applicability of the d i rect-contact concept for domestic hot water production, a PCM with a p hase change temperature of 59 C is chos en. To enable cost-efficient implementation of t h e storage system, a eutectic mixture o f two salt hydrates, magnesium chloride hexahydrate and magnesium nitrate hexa- hydrate, is chosen as the PCM. One ke y asp ect for the direct-contact concept is that, during discharge, the HTF channe l si nt h eP C Md on o tb e c o m ec l o g g e dd u r - ing the solidification of the PCM. In this study, the formation and topology of the channels in direct-contact system s under an optimized flow cond ition are investi- gated via visual observation and X-ray computed tomogr aphy. The elucidation of the channel structure provides information on the melting and crystallization behaviors of the PCM, which are shown schematically. KEYWORDS computed tomography, direct contact latent heat storage, heat transfer surface, latent heat storage, phase change material, thermal heat storage 1 | INTRODUCTION Because of the increasing demand for energy, the finite nature of fossil fuels, and concerns about environme ntal impacts, it is nece ssary to increase the use of re newable energy sources such as solar, biomass, and wind energies. Because of their temporary nature, the effective use of these energy sources depend s on the availabi lity of effi- cient energy s torage systems. 1 Because of the natural var- iability of sun and wind as heat and electricity sources, an effective storage technology is required to compensate for the time lag betwee n energy supply and demand. 2 Received: 24 September 2019 Revised: 10 January 2020 Accepted: 10 January 2020 DOI: 10.1002/er.5202 This is an open access article under the terms of the Creative Commons Attribution-NonCom mercial License, which perm its use, distribution and reproduction in any medium, provided the original work is properly cite d and is not used for comme rcial purposes. © 2020 The Authors. International Journal of Energy Resea rch published by John Wiley & Sons Ltd Int J Energy Res. 2020 ;44:5017 – 5025. wileyonlinelibrary.com /journal/er 5017 In this investigation, we focus on thermal storage sys- tems. There are three types of thermal energy storage sys- tems: sensible heat storage, latent heat storage, and thermochemical he at storage systems. 3 Despite their high energy storage densities of the reactants of approximately 500 kWh/m 3 , thermochemical stora ge systems have a major disadvantage in that the technology is complex and requires large investments. 4,5 In comparison with sensible heat storage systems, latent heat storage systems have the following advantages 6 : • Extraction and sup ply of thermal energy at an approxi- mately constant temperature • Approximately five times higher energy storage den- sity ( Δ ϑ =1 0 K ) For a solid/liquid phase change, phase change mate- rials (PCMs) can be subdivided into two main categories: inorganic and organic s ubstances. 7 Inorganic substanc es include salt hydrate s, salts, metals, and alloys, while organic substances include paraffins, nonparaffins, and polyalcohols. Organic nonp araffins include a variety of substances such as fatty acids. In add ition, eutectic mix- tures of inorganic and/or organic substances are also used as PCMs. 8 A large number of organic and inorganic substances have melting points in a te chnically relevant range and substantial enthalpies of fusion. Nevertheless, besides having a suitable melting point, the majority of PCMs does not meet the criteria for a suitable storage medium 9 as their enthalpy of fusion is too low or they are corrosive or simply too expensive. A recent overview of suitable PCMs is given in Zalba et al. 10 In this study, we focus on salt hydrates. Similarly, to paraffins and fatty acids, they have melting temperatures between 0 C and 100 C. Fatty acids were excluded because they are about three times more expensi ve than paraffins. 8 Compared with paraffins, salt hydrates have several advantages 11 : • High volumetric latent heat stora ge capacity (approxi- mately 200-600 kJ/L 3 ) • Low cost and widesprea d availability • Sharp phase change (paraf fins are mixtures of several hydrocarbons and thus have a melting temperatur e range rather than a sharp melting point as in the case of salt hydrates 8 ) • High thermal conductivity (paraffin of approximately 0.2 W/m 2 K 12 and salt hydrates of approximately 0.5 W/m 2 K 13 ) • Nonflammable However, salt hydrates also have some disadvantages, which make their use as a latent heat storage mediums more difficult 10 : • Undercooling: The liquid PCM cools to below the melting point of the PCM during energy removal with- out solidifying. • Phase separation can occur in PCMs that consist, for example, of several components. Dur ing a melting and crystallization cycle, it is possible that phases partially separate. The individual phases have different proper- ties, which also differ from the desired properties of the PCM. • Corrosion: Many inor ganic substances, as well as salt hydrates, are corrosive toward s metals. This must be considered during the construc tion of the stor- age tank. • Water sorption due to the hygroscopy behavior in many salt hydrates leads to changes of the stoichio- metric water content reducing the phase change enthalpy. To improve the performance of latent heat storage systems with salt hydrates as PCMs, nucleating agents and thickeners help to prevent both undercooling and phase separation. 1 In 1957, Etherington suggested another solution for the problems of undercooling and phase separation. 14 In this approach, the storage mate- rial, the salt hydrate (disod ium phosphate dode- cahydrate), and the heat transfer fluid (HTF) (oil) are in direct contact, and the media are not miscible. The HTF is injected into the lower part of the storage tank and rises through the liquid PCM in the form of droplets, as the density of the HTF is lowe r than that of the PCM . Because of the resulting agitation, undercooling and phase separation of the PCM are reduced. FIGURE 1 Schematic illustration of a direct-contact latent heat storage system 15 5018 KUNKEL ET AL . In this study, a direct-contact latent heat storage sys- tem employing a eutectic mixture of two salt hydrates as the PCM, namely, magnesium chloride hexahy drate and magnesium nitrate hexahydrate, and a mineral oil as the HTF is investigated. Figure 1 illustrates a direct- contact latent heat storage tank. In Figure 1, the PCM is in a completely melted state; that is, the storage system is loaded. If oil at a tempera- ture below the melting temperature of the PCM is injected into the storage tank, the PCM cools down and begins to crystallize in the vicinity of the oil droplets. During this crystallization process, a channel structure is formed in the PCM. If the PCM is completely crystallized, a channel structure remains within the PCM. In this state, the storage tank is discharged. To charge the system again, oil at a temperature above the melting temperature of the PCM is pumped through the channel structure to liquify the PCM. Besides direct-contact systems, indi rect-contact latent heat storage systems have also been described in the liter- ature. 16-18 In these systems, the PCM and the HTF are physically separated by a wall. For instance, a piping s ys- tem for the HTF separates it from the PCM . Compared with indirect heat transfer, direct heat transfer offers the following advantages 3,19,20 : • Higher charging and discharging rates due to improved heat transfer between the PCM and the HTF • Higher storage density, since there is no piping system in the storage tank • Extended period of high transfer rate during charge because solidified PCM with low therm al conductivity around the piping system does not screen the heat transfer Further studies on direct-contact latent heat storage systems are described in the literature. 14,15,20-37 In these studies, only a few simplified descriptions of the melting and crystallization behaviors are given. 34,36 In particular, the determination of heat transfer surfaces has not been described. To support a deeper understanding of direct heat transfer and the design of the storage system, this study provides a detailed explanation of the melting and crys- tallization behaviors of the PCM. The investigation is based on volumetric images from the H TF channels recorded by X-ray computed tomography (CT). The heat transfer surface is then subsequently determined directly from the images for one model storage tank. For the design of the storage tanks, however, it is of interest to understand how the heat transfer surface is distributed in the PCM. This allows conclusi ons to be drawn about which areas melt quickly and which areas melt slowly. To facilitate the X-ray analysis, a model storage tank was built, which has only one oil inlet at the bottom. The internal surface area is an important property for any heat exchanger, therefore this studies goal is to advance the design and s cale up of direct-contact PCM heat storage systems. 2 | MATERIAL AND METHODS 2.1 | Phase change material The PCM used was a stable eutectic mixture of the two salt hydrates: magnesium chloride hexahydrate and mag- nesium nitrate hexahydrate. The PCM has a melting point of 59 C and is well suited for storing heat from renewable energy sources or for storin g low-temperature waste heat. The mineral oil Fragolt herm Q-7, which is optimized for cooling and heating in process engineering plants, was employed as an HTF. Table 1 shows the prop- erties of the PCM and the mineral oil. The support material of the storage tank is also required for the investigation of the channel structure by means of X-ray CT. Therefore, polycarbonate was selected for this pu rpose. 2.2 | Experimental setup and measurement method The experimental setup shown in Figure 2 was used for the investigation of the channel geometry. The set up con- sists of an oil receiver tank (A), an electrical gear pump TABLE 1 Material properties of the PCM and mineral oil as the heat transfer fluid (HTF) PCM Oil Melting point, C5 9 38 Less than − 40 Heat of fusion, kJ/kg 132.2 38 Not relevant Heat capacity solid, kJ/kg K 1.86 (40 C) 38 Not relevant Heat capacity liquid, kJ/kg K 2.42 (70 C) 38 2.257 (70 C) 40 Heat conductivity solid, W/m K 0.678 (53 C) 38 Not relevant Heat conductivity liquid, W/m K 0.510 (65 C) 38 0.123 (70 C) 40 Density liquid, kg/m 3 1550 38 797 (70 C) 40 Density solid, kg/m 3 1630 38 Not relevant Viscosity, mPa s 35 (62.5 C) 39 4.51 (50 C) 40 Abbreviation: PCM, phase change material. KUNKEL ET AL . 5019 (B) delivering a pressure drop-independent mass flow, two heat exchangers (C and D), and the storage tank (E) containing the PCM . The storage tank is made of transparent polycarbonate and has a height of 350 mm and an internal diameter of 40 mm. The transparent polycarbonate mak es it possible to obs erve the melting and crystallization behaviors. At the bottom of the stor- age tank, there is one orifice with a diameter of 6 mm, which allowed the input of oil into the storage tank. Two different channel configurations were investigated: an artificially created cylindrical chan nel and a channel under real flow conditions. The artificial cylindrical channel had a diameter of 6 mm and was created usin g a cylindrical inset. This channel geometry serves as a vali- dation method for the measurement and evaluation method, as the shell surface can be calculated based on the known geometry. To measure the pressu re and oil temperature in the pipeline, a pressure transmitter and eight thermocouples (type K) were integrated. To create the artificial cylin dri- cal channel, a steel pipe with an outer diameter of 6 mm was inserted into the oil inlet opening in the bottom of the storage tank containing the liqui d PCM. Subse- quently, oil was intr oduced at a temperature below the melting point of the PCM, such that the PCM began to crystallize on the wall of the steel pipe. Onc e the entirety of the PCM had crystallized, it was possible to remove the pipe, and a chan nel with an inner diameter of 6 mm remained inside the PCM. To create a channel under real flow conditions, complete melting of the PCM is required. The PCM was overheated to a temperatur e of approximately 68 C, and oil at a temperature of 49 C was then injected into the storage tank. The oil mass flow was set to 6.50 10 − 4 kg/s. The PCM then cooled down to its melting point, and crystallizat ion began. In this case, a branched channel structure is formed within the PCM . To investigate the channel structure, the entire storage tank was removed from the experi mental setup. Subse- quently, the channel structure was investi gated by means of X-ray CT. The XT H 225 ST CT system from Nikon was used for this pu rpose. The X-ray radiation was gener- ated with a rotating anode tube with a maximu m acceler- ation voltage of 225 kV. For the measurement of the storage system, an acceleration voltage of 120 kV and a tube current of 550 μ A were employed. The storage sys- tem was measured in two overlapping segments (top and bottom), with a field of view of 2000 × 2000 pixels recorded by the X-ray detector . The cross-sectional images were subsequently reconstructed by the Nikon reconstruction software, based on the Feldkamp-Davis- Kress algorithm. 41 The dimension of the storage tank resulted in a reso- lution of 93 μ m. After the measurement started, the sam- ple stage rotated 360 , and images were taken continuously during the measurements. After approxi- mately 38 minutes, the measur ement was finished. The images of the two consecutive measurements were then combined manually by matching the two image stacks according to position and prominent features. 2.3 | Evaluation method The volumetric images were analyzed by the Volume Graphics Studio Max 3.1.2 software from Volume FIGURE 2 Schematic of the experimental setup 37 : A, oil receiver tank; B, pump; C, cooling; D, heating; E, storage tank 5020 KUNKEL ET AL . Graphics (Heidelberg, Ger many). The channel visualiza- tion and analysis of the heat tran sfer surface were per- formed with the inclusion module. The selection threshold for the analysis process wa s based on the inte- grated automatic threshold procedure. The program myVGL from Volume Graphi cs was subsequently employed to measure and display individual chann el- specific conditions, such as the local diameter of the channel. 3 | RESULTS AND DISCUSSION 3.1 | Channel formation during solidification Figure 3 shows the crystallizat ion behavior schematically. At the be gi nnin g of the so li dif ic at io n behav io r, th e PCM is com pl et el y melt ed , and the oil ris es in the P CM in the f or m of dro pl et s (Fig u re 3 A) . Th e oil en te rs t he st or ag e tan k in t he fo r m of a je t, wh ic h is fo ll ow ed by de cay of th e jet . Af te r th e de ca y, si ngl e o il dr opl et s ar e f orme d. By int ro du ci ng oil at a te mper at ur e belo w the ph as e cha nge temp er at ur e of the PC M, the PC M begi ns to c ool do wn . Su bseq ue nt ly , the PCM st ar ts to so li di fy, wher eb y so me soli d PC M pa rt ic les fo rm in th e li qu id PC M. In ad di ti on , a la ye r of soli d PC M is forme d at t he PC M/ oil ph as e bo un d- ary at th e uppe r pa rt of the st ora ge t ank. Th is la ye r ap pear s as a kind o f fo am. Th e re ma in in g por ti on of the soli d PC M is kept in su sp en si on by the oi l flow . So me soli d PCM pa rt ic le s sink to the bo tt o m of the sto ra ge tan k bec au se th e so li d pa rt ic le s hav e a h ig he r de nsi t y tha n th at of the li qu id PCM. In t he lowe r pa rt of the st ora ge ta nk, the oil je t for ms a sing le cyli nd r ic al chan ne l. Ov er time , an inc re as in g amoun t of soli d PCM par ti cles ar e for me d, whic h ar e kept in susp en si on (F ig ure 3B ). Be ca use of th e fo rmat io n of soli d PCM part ic le s, the oil fl o w is hind er ed ; this fl o w resi st an ce in cr ea ses wi th hei gh t in the st or ag e tan k. Ne ve rt he le ss, in the mi dd le of the sto ra ge t an k, th e je t deca y ca n st il l form a st r ongl y br an che d ch an nel st r uc- tur e. Howe ve r , in th e to p pa rt , th e hi ndr an ce is so st ro ng tha t on ly a main cha nne l is fo rmed . Fi nal ly , the PCM so lidi fi es c om pl etel y (F igu re 3C ). In order to determine the channel structure, the solid- ified storage tank was transferred to an X-ray CT system where a stack of volumetric images were obtained and recombined. Figure 4 shows the channel structures of the artificial cylindrical channel (Figure 4A) and of one chan- nel under real flow conditions (Figure 4B) within the PCM, obtained by means of the CT system. Figure 4 shows a visualization of the channels extracted from the X-ray CT images. Figure 4A displays the storage system with the artificial cylindrical channel. The optical analysis revealed that the ave rage diameter was 6.20 mm (±0.08 mm) and the shell surface was 93.65 cm 2 . With a height of 319 mm, the surface area of the shell should therefore be 62.13 cm 2 (±6.55 cm 2 ). The discrepancy with the measured shell surface can be explained by the surface roughness of the chann el wall. Figure 4B presents the visualization of the structure of the channel, which was created under real flow condi- tions. Beginning at the oil inlet, a nearly cylindrical section of the channel with a height of approximately 90 mm and a diameter of approximately 2.4 mm (±0.2 mm) can be observed. The heat transfer surface was approximately 6.8 cm 2 . This section is genera ted by the oil jet resulting from the oil mass flow. The jet then decays, which causes a branch to form within the PCM. In the next section (beginning at a height of about 110 mm), the structure is heavily branched. It is in this section that the largest heat transfer area is provided. This section is succeeded by another (between 260 and 320 mm), in which the individual branc hed channels rec- onnect. The numb er of branches is thereby reduced. In contrast to previously reported findings, 36 an uneven channel structure was formed. This structure fundamen- tally influences the melting of the PCM . In this example, the shell surface of the channel was 168.1 cm 2 , which also corresponds to the heat transfe r surface. FIGURE 3 Schematic illustration of the crystallization behavior of the phase change material (PCM) in three different phases: A, initial situation, where PCM is completely melted; B, intermediate situation, where solid and liquid phases of the PCM coexist; C, storage tank in the discharged state, where PCM is solid KUNKEL ET AL . 5021 FIGURE 4 Visualization of the structures formed under real flow conditions within the phase change material (PCM), obtained by means of the X-ray computed tomography (CT) system of the following: A, the artificial cylindrical channel; B, a channel FIGURE 5 Schematic illustration of the melting behavior of the phase change material (PCM) divided into six different phases. A, Initially, the PCM is completely solid. B, The channel structure expands via melting of the PCM and formation of a liquid PCM layer at the channel outlet. C, The channel structure expands further, and the liquid PCM layer at the channel outlet grows as well. D, The threshold diameter is reached, at which point the liquid PCM flows back into the channel structure. E, In the melting process, the middle section melts first. F, The storage tank is then in a charged state, wherein the PCM is liquid 5022 KUNKEL ET AL . 3.2 | Melting behavior Figure 5 schematically shows the melting behavior of the PCM. At the beginn ing of the char ging proces s, the PCM is complete ly solidified, and a channel s t ructure is present wi t h in t h e P C M. T h e oi l t h e n f lo w s t hr o u gh t h e pr ev al ent channel structure, and the channels are comp letely filled with oil (Figure 5A/ Figure 3C). By injecting oil with a tem- perature above the melting temperature of the PCM into the system, the PCM heats up and b egins to me lt . Convec- tive heat transfer oc curs, and the channel structure expands. The oil flow partially rem oves liquid P CM from the canal. This res ults in the formation of a liquid PCM la ye r at th e ch an nel ou tl et (Fi gu re 5B). T he cha nn el str uc - ture continues to expand, and the laye r of liquid PCM also continue s to grow (Figure 5C). If the channel st ructure reaches a threshold diamete r , the layer of liquid PCM flows back into the ch annel stru cture. The cha nne ls a re then filled with liquid PCM. In consequence, an oil jet forms, which is followed by decay of the jet and the formation of single oil droplets. The liquid PCM is further heated by the oil, while the liq u id PCM m elts the solid PCM via conduc- tive heat transfer (Figure 5D). Further areas of the PCM are melted by this additional s upply of heat. From optical recordings of th e charging pro cess, it can be s een that the mi dd le sec t io n of t he st or a ge sy s t em f ir st me l t s co mpl et e ly , followed by the lower section. The PCM/ oil phase bound- ary is within the channel structure (Figure 5E) . Eventually, the top section is melted until the entire PCM is in the liq- uid s t ate (F igure 5F). Figure 6 sh ows a photog raph of the intermediate state illustrated in Figure 5E. Figure 6 confirms that the PCM in the m iddle section of the storage tank had already melted while the PCM in the top a nd bottom sect ions was still solid. From a qualitative point of view, this s tate provides the largest heat transfer surface. Although the heat transfer surface is r e d u c e di nc o m p a r i s o nw i t ht h e m i d d l es e c t i o n ,t h el o w e r pa rt o f th e PCM me lt s sub se qu ently. This may be explained by the high heat flux in this area due to the highest temper- ature gradient b etween the oil and PCM. Finally, the PCM in the top section melts as the rest of the PCM is already liquid. The individual channels have merged by this sta ge, to form a main chann el. The he at transfer surface is small. Previous studies have described and discussed, 20,31 among other thin gs, the melting and crystallization behaviors of PCMs. This publication supports our fin ding that the middle section melts first. These results suggest that an efficient storage system should have a low height in order to reduce the area in the top section of the stor- age tank wherein PCM is solid (Figure 6). As a conclu- sion, it can be said that direct-c ontact latent heat storage tanks should be built wider rath er than taller. It is not expected that the residence time of the oil within the PCM would be insufficient to achieve efficient heat trans- fer in shorter systems. A direct-contact latent heat storage system employing erythr itol (density 42 : 1480 kg/m 3 ) and an oil as the HTF has been described previously. 36 In this study, it was shown that efficient heat transfer can be achieved even with PCM heights as low as 0.2 m. For initial designs, a total PCM height of approxi- mately 0.30 m is therefore recommended, even for larger storage tanks. 4 | CONCLUSIONS In this study, the melting and solidification behaviors of a PCM within a direct-contact latent heat storage system were experimentally investigat ed. The considered system consisted of a vertical cylindrical storage tank conta ining a eutectic mixture of two salt hydrates as the PCM and FIGURE 6 Image of the state illustrated in Figure 5E KUNKEL ET AL . 5023 a mineral oil as the HTF. By combining visua l observa- tions with a volumetric cross-sectional analysi s by X-ray CT, the melting and solidification behaviors were eluci- dated, and design principles for such storage systems were visualized, derived, and proposed. The conclusions are summarized as follows. Visual and X-ray CT inspections confirmed a hierar- chical melting behavior. The middle section of the PCM melted first, followed by the bottom section , and finally the top section. During the solidification behavior, a channel structure providing an increased heat transfer surface is formed in the middle section. The total surface area was 168.1 cm 2 in the investigat ed geometry. The X-ray CT images confirme d that the channel structure was divided into three sections: an unbranche d section in the lower part of the PCM , succeeded by a strongly branched section in the middle, and a less branched section at the upper part. With the help of these images, the melting and crystallization behaviors were illustrated in detail. For the design of direct-co ntact latent heat storage systems, it is recomm ended to build storage systems wider rather than taller, as the channel structure in the upper part of the PCM is less branc hed and the heat transfer surface is thereb y reduced. This can lead to del- ayed melting and reduce d storage performance. The elucidation of the m elting and crystallization dynamics was an important undertaking to deepen the understanding o f direct heat trans fer and will assist greatly in t he d esi gn o f dir ec t-c ont ac t lat en t h ea t st o ra ge sy st ems . ACKNOWLEDGE MENTS The authors acknowled ge Prof Dr Christoph Zollikofer and Dr Jody Weissmann for proving the possibility to perform the computed tomography experiment s at the facilities of University of Zurich. NOMENCLATU RE d c diameter of the PCM channel (mm) d s diameter of the storage tank (mm) ABBREVIATIONS CT computed tomograp hy HTF heat transfer fluid P pressure gauge PCM phase chan ge material T thermocouple ORCID Frederik Wunder https://orcid.org/0000-00 03-3990- 8297 Stefan Krimmel https://orcid.org/0 000-0002-5462-2548 REFERENC ES 1. Dincer I, Rosen MA. Thermal Energy Storage: Systems and Application . Second ed. United Kingdom: Wiley; 2011. 2. Tamme R, Jossen A, Henning H-M. 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