Robotic hand model parameters.
\\n\\n
Dr. Pletser’s experience includes 30 years of working with the European Space Agency as a Senior Physicist/Engineer and coordinating their parabolic flight campaigns, and he is the Guinness World Record holder for the most number of aircraft flown (12) in parabolas, personally logging more than 7,300 parabolas.
\\n\\nSeeing the 5,000th book published makes us at the same time proud, happy, humble, and grateful. This is a great opportunity to stop and celebrate what we have done so far, but is also an opportunity to engage even more, grow, and succeed. It wouldn't be possible to get here without the synergy of team members’ hard work and authors and editors who devote time and their expertise into Open Access book publishing with us.
\\n\\nOver these years, we have gone from pioneering the scientific Open Access book publishing field to being the world’s largest Open Access book publisher. Nonetheless, our vision has remained the same: to meet the challenges of making relevant knowledge available to the worldwide community under the Open Access model.
\\n\\nWe are excited about the present, and we look forward to sharing many more successes in the future.
\\n\\nThank you all for being part of the journey. 5,000 times thank you!
\\n\\nNow with 5,000 titles available Open Access, which one will you read next?
\\n\\nRead, share and download for free: https://www.intechopen.com/books
\\n\\n\\n\\n
\\n"}]',published:!0,mainMedia:null},components:[{type:"htmlEditorComponent",content:'
Preparation of Space Experiments edited by international leading expert Dr. Vladimir Pletser, Director of Space Training Operations at Blue Abyss is the 5,000th Open Access book published by IntechOpen and our milestone publication!
\n\n"This book presents some of the current trends in space microgravity research. The eleven chapters introduce various facets of space research in physical sciences, human physiology and technology developed using the microgravity environment not only to improve our fundamental understanding in these domains but also to adapt this new knowledge for application on earth." says the editor. Listen what else Dr. Pletser has to say...
\n\n\n\nDr. Pletser’s experience includes 30 years of working with the European Space Agency as a Senior Physicist/Engineer and coordinating their parabolic flight campaigns, and he is the Guinness World Record holder for the most number of aircraft flown (12) in parabolas, personally logging more than 7,300 parabolas.
\n\nSeeing the 5,000th book published makes us at the same time proud, happy, humble, and grateful. This is a great opportunity to stop and celebrate what we have done so far, but is also an opportunity to engage even more, grow, and succeed. It wouldn't be possible to get here without the synergy of team members’ hard work and authors and editors who devote time and their expertise into Open Access book publishing with us.
\n\nOver these years, we have gone from pioneering the scientific Open Access book publishing field to being the world’s largest Open Access book publisher. Nonetheless, our vision has remained the same: to meet the challenges of making relevant knowledge available to the worldwide community under the Open Access model.
\n\nWe are excited about the present, and we look forward to sharing many more successes in the future.
\n\nThank you all for being part of the journey. 5,000 times thank you!
\n\nNow with 5,000 titles available Open Access, which one will you read next?
\n\nRead, share and download for free: https://www.intechopen.com/books
\n\n\n\n
\n'}],latestNews:[{slug:"intechopen-authors-included-in-the-highly-cited-researchers-list-for-2020-20210121",title:"IntechOpen Authors Included in the Highly Cited Researchers List for 2020"},{slug:"intechopen-maintains-position-as-the-world-s-largest-oa-book-publisher-20201218",title:"IntechOpen Maintains Position as the World’s Largest OA Book Publisher"},{slug:"all-intechopen-books-available-on-perlego-20201215",title:"All IntechOpen Books Available on Perlego"},{slug:"oiv-awards-recognizes-intechopen-s-editors-20201127",title:"OIV Awards Recognizes IntechOpen's Editors"},{slug:"intechopen-joins-crossref-s-initiative-for-open-abstracts-i4oa-to-boost-the-discovery-of-research-20201005",title:"IntechOpen joins Crossref's Initiative for Open Abstracts (I4OA) to Boost the Discovery of Research"},{slug:"intechopen-hits-milestone-5-000-open-access-books-published-20200908",title:"IntechOpen hits milestone: 5,000 Open Access books published!"},{slug:"intechopen-books-hosted-on-the-mathworks-book-program-20200819",title:"IntechOpen Books Hosted on the MathWorks Book Program"},{slug:"intechopen-s-chapter-awarded-the-guenther-von-pannewitz-preis-2020-20200715",title:"IntechOpen's Chapter Awarded the Günther-von-Pannewitz-Preis 2020"}]},book:{item:{type:"book",id:"1375",leadTitle:null,fullTitle:"Hemodialysis - Different Aspects",title:"Hemodialysis",subtitle:"Different Aspects",reviewType:"peer-reviewed",abstract:"The book provides practical and accessible information on all aspects of hemodialysis, with emphasis on day-to-day management of patients. 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\r\n\tCardiovascular diseases and finally heart failure (HF) are still the primary cause of death worldwide mainly due to poor treatment strategy. Cardiac hypertrophy is one of compensatory mechanisms against some cardiovascular issues, especially H or hypertension, but it is also the primary risk factor for HF development. Heart failure is the final stage of many cardiovascular diseases. The progression mechanism of HF from the cardiac hypertrophy is poorly understood. Clarification of this mechanism will provide new insights into the development of effective treatment. Our current understanding leads to the symptomatic therapy.
\r\n\r\n\tThis book will present the molecular pathways distinguishing beneficial from maladaptive hypertrophy. Therefore, both laboratory and clinical studies should be included to provide attractive biological targets in the treatment of HF. It will provide the mechanism related to neurohormonal modulation resulting in edema, fatigue, and reduced patient’s quality of life and increased mortality risk; the molecular mechanism that affects the heart function leading to HF.
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She worked as a postdoctoral researcher at New York University for two years. She has published more than twenty articles and four international book chapters. She has also edited a book. 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This requires extensive analysis of developing trends in scientific research in order to offer our readers relevant content. Creating the book catalogue is also based on keeping track of the most read, downloaded and highly cited chapters and books and relaunching similar topics. I am also responsible for consulting with our Scientific Advisors on which book topics to add to our catalogue and sending possible book proposal topics to them for evaluation. Once the catalogue is complete, I contact leading researchers in their respective fields and ask them to become possible Academic Editors for each book project. Once an editor is appointed, I prepare all necessary information required for them to begin their work, as well as guide them through the editorship process. I also assist editors in inviting suitable authors to contribute to a specific book project and each year, I identify and invite exceptional editors to join IntechOpen as Scientific Advisors. 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The robotic hand is the main interactive part of the environment with the service robotics [2, 3]. Grasping operation [4] has been used explicitly in robotic hand during the interactive period which represents the process of holding objects via two stages: free motion and constrained motion. Free motion is the moving of fingers before detecting the grasped object, and the constrained motion is the state of fingers when the object is detected. The common purpose in grasping is to handle unknown objects. Thus, finding both a model system and a control algorithm to deal with non-predefined objects is essential in a robotic hand. Regarding modeling, interactional modeling is the demand to perform a specific control algorithm. With interactional modeling, the contact force between the robotic hand and the grasped objects has obtained without needing their properties. In control point of view, the robotic hand holds an object by its fingers and moves the object to another place. In this case, there are different modes of operation which can be listed as before holding the grasped object, holding the grasped object, and moving the robotic hand while holding the grasped object. The aim at each mode is distinct to the others and has to respond to the operation assigned. Thus, the multitude of various goals which have to be achieved with regard to the various operations presents an interesting scenario in the control of a robotic hand.
\nGenerally, it is essential to obtain the modeling of a multi-fingered robotic hand before implementing a specific model-based control algorithm. Arimoto et al. [5] presented a two-fingertip grasping model to control the rolling contact between the fingertips and the grasped object. Arimoto et al. derived the model through the use of the Euler-Lagrange equation with respect to the geometry of the fingertips which is represented by the arc length of a fingertip. Corrales et al. [6] developed a model for a three-fingered robotic hand; in their study the transmission of fingertip contact force from the hand to the grasped object is considered. Boughdiri et al. [7] discussed the issue of modeling a multi-fingered robotic hand as a first step, before designing controllers. They considered free motion only, without the constraints of grasped objects. In a proceeding work, Boughdiri et al. later [8] considered the constraints of grasped objects and the coupling between fingers in grasping tasks.
\nIn the control scenario of a robotic-environment interaction, there is generally also a similar case of a robotic hand-grasped object interaction; force tracking is necessary to obtain appropriate and safe contacts. In force tracking, three main position-force controllers are introduced: stiffness control, hybrid position/force control, and impedance control [9]. Among the above three controllers, impedance control presents an integrated process to constrained manipulators [10]. The impedance controller is introduced by Hogan in 1985 to set the dynamic conduct between the motion of the robot end-effector and the contact force with the environment, instead of regarding the control of motion and force individually [11, 12]. Chen et al. [13] derived impedance controller for an elastic joint-type robotic hand in Cartesian and joint spaces. Chen et al. focused on the compensation of gravity and managing the parameter of uncertainties. Huang et al. [14] proposed the impedance controller for grasping by two fingers to deal with the problem of dropping objects when grasping by one finger. Zhang et al. [15] proposed an adaptive impedance controller with friction compensation to track forces of the multi-fingered robotic hand.
\nHowever, the synthesis of impedance control design continues to exist as a major challenge in the performance advancement of robotic hand in order to provide safe and robust grasping. Besides this, the greatest problems in robotic hand-grasped object interaction are the existence of nonlinearity in the dynamic system, dealing with different grasped objects, disturbances, and interference. In the previous studies, the aforementioned problems have not taken in consideration. The aim of this paper is to treat these problems using interactional modeling and the design gains of impedance control. The action of the suggested control expression is to provide a fingertip interactional robust control algorithm that takes into account the dynamics of the robotic hand under unknown contact conditions. To accomplish this, we propose first to linearize the dynamics on the level of position-tracking controller through six PD controllers. When executed, the calculated gains of the designed PD controllers result in zero steady errors without overshoot. Second, through an impedance controller, the interactional fingertips’ force is regulated by the robotic hand’s impedance. The gains of the impedance are designed based on genetic algorithm. As a result, the introduced control expression enables the position and velocity of fingertips to be controlled simultaneously without changing over control subspace. This control expression avoids selecting between different controllers which causes indirect control and consumption of high energy. The operation and the robustness of the presented control expression are approved by MATLAB/Simulink in several tests.
\nThe rest of the chapter is organized as follows. In Section 2, the mathematical representation of kinematics and dynamics of the robotic hand with environment interaction is derived and explained. In Section 3, the overall controllers of position tracking and impedance control are designed. In addition, the suggested procedure of obtaining optimum values of impedance gains using genetic algorithm is explained. In Section 4, following the joint path and fingertip position is tested. Then, the robustness of the system is examined. Finally, the conclusions of this study are presented in Section 5.
\nThe models of a robotic hand system are the mathematical equations that describe all the contact forces and motion of the fingers at any time [16]. These models are essential for grasping and manipulation operations which include kinematics, dynamics, and contacts between the fingers and the environment. A multi-fingered robotic hand with an existing grasped object has a complex structure. Thus, deriving the mathematical representation is not a simple task. In this section, the mathematical representation for a two-fingered robotic hand with an environment is developed. Changing the orientation of the robotic hand with respect to the inertial (earth) frame during manipulation operation is considered in this analysis.
\nThe system is a two-fingered robotic hand that can adjust fingertip grasp forces by the torque of actuators in the joints. Each finger includes three joints (MCP, PIP, and DIP) and three rigid phalanges (proximal, intermediate, and distal). The motion of the finger actuates through the torque in the joints. The variables \n
Coordinate frames of the robotic hand.
The result of orienting the robotic hand with respect to the earth coordinates is expressed by defining the three rotation angles roll, pitch, and yaw (RPY). In which, roll is (\n
where \n
Forward kinematics is implemented here to express the relationship between the Cartesian spaces of the fingertip contact points, which are represented by coordinates (\n
and the forward kinematic of finger 2 is
\nwhere \n
where \n
and
\nThe robotic hand transforms the generated torque by each joint to the wrenches exerted on the grasped object through the following Jacobian matrix:
\nA contact interaction, which uses contact behavior between rigid fingertips and a flexible grasped object, is proposed in this study (see Figure 2). The grasped object is assumed as a linear spring of stiffness \n
where \n
Side view of fingertip contact interaction system on the x-axis.
The motion equations are derived to describe the dynamics of the robotic hand when interacting with the grasped object; the explained fingertip forces in Eqs. (10)–(12) are involved in the dynamic equation. When ignoring friction, each finger in free motion can be described by the following general motion equation:
\nwhere \n
where \n
\n\n
to derive Eqs. (15) and (16), the Lagrange equations of motion are used. For each finger manipulator, the equation of motion is given by [18]
\nwhere \n
the position of the mass center of intermediate phalanx with respect to MP joint is represented by
\nand the position of the mass center of distal phalanx with respect to MP joint is represented by
\nwhere \n
and to obtain the kinetic energy, the above formulas (\n
where
\nThe procedure for calculating \n
by using the kinetic energy in Eq. (18) and the potential energy in Eqs. (25)–(27), it results that Eqs. (19)–(21) after being rearranged in a matrix form result in
\nThe formula of matrices’ elements in Eq. (28) is listed in Appendix A. From Eqs. (15) and (16), the overall dynamics of robotic hand can be constituted as
\nwith the following matrix forms;
\nThus, the six motion equations are presented by rearranging Eq. (29) to result in
\nThe desired finger configuration in joint space can be obtained by solving the above equation, which will be explained later in Section 3.1 for designing the position-tracking controller.
\nThe derived mathematical representation is applied using MATLAB/Simulink to implement the proposed controllers and the tests of this study. The parameters of the model, which are used in Simulink, are shown in Table 1. The overall controllers of the robotic hand are depicted as a complete block diagram in Figure 3. In the following sections, the design of the controllers is described in detailed.
\nParameter | \nValue | \nParameter | \nValue | \n
---|---|---|---|
\n\n | \n\n\n | \n\n\n | \n\n\n | \n
\n\n | \n\n\n | \n\n\n | \n10 mm | \n
\n\n | \n\n\n | \n\n\n | \n\n\n | \n
\n\n | \n7083 g.mm2 | \n\n\n | \n400 g.mm2 | \n
\n\n | \n\n\n | \n\n\n | \n100 mm | \n
\n\n | \n\n\n | \n\n\n | \n50 mm | \n
\n\n | \n\n\n | \n\n\n | \n70 mm | \n
\n\n | \n1125 g.mm2 | \n\n | \n |
Robotic hand model parameters.
Block diagram of the complete robotic hand controllers.
Recently, a variant of the PD controller explicitly has been considered in the control of nonlinear system where the aim is to make the system follow a specific trajectory [19, 20, 21, 22]. The joint angle controller shown in Figure 3 is the inner feedforward loop which presents the effect of the input torque on the error in Eq. (30). The detailed block diagram of this controller is shown in Figure 4. The tracking error is formed by subtracting the joint angle vector (\n
PD joint angle controller for each finger.
The objective is to minimize this error at any time, by differentiating Eq. (31) twice, solving for \n
where \n
where \n
The system can be stabilized in Eq. (34) by a proper design of PD controller to track the error \n
where \n
The design of gains is selected for the closed-loop time constant (\n
where \n
The stability of robustness analysis by Lyapunov’s direct method is implemented here to verify the ability of applying the proposed PD controller in real situations where unmodeled disturbances are included in the actual robotic hand. The effect of unmodeled disturbances in robotic manipulator can be represented by replacing the PD controller gain matrices with matrices of nonlinear gains [23]. Considering the nonlinear matrices gains, the robotic hand input in Eq. (34) becomes
\nwhere \n
The stability of Eq. (32) together with Eq. (36) is assumed if there exists \n
The stability analysis is implemented by proposing the following Lyapunov function:
\nConsidering the smallest eigenvalues \n
thus
\nwhere \n
Then, Eq. (38) becomes
\nThe first two terms of Lyapunov function are positive. Regarding the third and the fourth terms, according to Eqs. (39) and (40), we have
\nthus
\nEquations (44) and (45) result in
\nand
\nHence, the Lyapunov function presented in Eq. (38) is globally positive definitive function.
\nTaking the derivative of Eq. (38) with respect to time, we get
\nFinally, using the rule of Leibnitz for representation, the integrals in differentiation form and Substituting Eq. (37) in (50) yield
\nfor all positive values of gain matrices \n
In this way, the system is globally exponential stabile.
\nThe PD impedance controller has been widely applied in modern researches for controlling the interaction with the environment [24, 25]. The fundamental principle of the implemented impedance control in this study is that the fingers should track a motion trajectory, and adjust the mechanical impedance of the robotic hand. The mechanical impedance of the robotic hand is defined in terms of velocity and position as
\nBy virtue of the above two equations, the fingertip contact force \n
where \n
where \n
where
\nand
\nHence, the contact forces are regulated in joint space, and the robotic hand can adapt the collision of the fingers with the grasped objects.
\nThe application of Lyapunov function technique determines the conditions of stability of impedance controller [26]. In the forward kinematic model, the equations of fingers are
\nOn the other hand, the errors are given as
\nwhere \n
where \n
then, we get
\nThe error dynamics in Eqs. (61) and (62) is asymptotically stable if the following candidate Lyapunov function
\nsatisfies the following conditions:
\nThe derivative of Eq. (70) is
\nEquations (61) and (62) can be rearranged as below
\nBy substituting Eqs. (72) and (73) in Eq. (71) and applying the relations in Eqs. (57)–(60), it yields
\nHence, the robotic hand system is asymptotically stable under the following boundaries:
\nor
\nGenetic algorithm is a well-known optimization procedure for complex problems which ascertains optimum values for different systems [27]. The genetic algorithm is written to find the optimum impedance gains. The code takes the calculated data from the robotic hand Simulink model to compute impedance’s gains. However, the detailed genetic algorithm that is applied in the design of the gains can be defined by the following proceedings:
\n(1) Generate a number of solutions. This represents the random number of population which includes the gains \n
(2) Fitness function. During the running of the program, the fitness is evaluated for each individual in the population. In this study, the objective of the fitness function is to minimize the errors \n
where \n
(3) Create the next generation [28]. At each step, genetic algorithm implements the following three rules to create a new generation of the recent population:
Individuals called parents are selected by the selection rules, and then the population of the next generation is obtained by contributing the parents.
Two parents are combined to generate children by crossover rules for the next generation.
Children are formed by mutation rules. The process of forming children is dependent on applying random changes on the individual parents.
(4) Setting the genetic algorithm. The following parameters are used for setting the proposed genetic algorithm in this study: the number of generations = 80, the size of population = 30, and the range of gains are \n
The obtained interactional model was applied in the simulation to verify the designed controllers through three tests as follows:
Test 1: Following a specific joint path.
Test 2: Following fingertip position.
Test 3: Robustness of the controllers.
The Simulink model is implemented using MATLAB as shown in Figure 5.
\nThe Simulink model of the robot hand.
This test is focused on position-tracking performance of joints. We assumed the two fingers are in initial position (\n
The simulation result explained in Figure 6 shows that the designed position-tracking controller can follow a specific path with zero steady error and without overshoot. A unit step input function of amplitude \n
Joint tracking of sine wave path.
Tracking errors of finger 1 joints.
The second test is implemented to monitor the operation of the designed impedance controller in task space. We assumed the initial position of the fingertip 1 is (135, 100, −25 mm) and it has to reach the position (115, 153.7, −25 mm). The position of the grasped object is assumed at \n
Motion of fingertip 1 with impedance controller.
Fingertip contact force with the grasped object.
For comparison purposes, another study is implemented without considering the impedance controller in the overall control loop, i.e., \n
Motion of fingertip 1 without impedance controller.
The robustness of the designed controllers is checked in this section. This test is implemented within the same parameters of the desired position and object location in the test of Section 4.2. The disturbances on the robotic hand cause change of the fingertip contact forces. Here, we assumed that the disturbances result in a contact force with a white Gaussian noise [29, 30, 31, 32] shown in Figure 11. The Gaussian noise model is generated using block AWGN channel in Simulink. The position of the AWGN channel is shown in Figure 5. The parameters of white Gaussian noise are set as shown in Figure 12. The designed controllers have achieved the functionality of rejecting the disturbances and kept the motion of the finger as shown in Figure 13.
\nContact force signal with a white Gaussian noise.
Parameters of the applied white Gaussian noise.
Response of the designed controllers to the disturbances.
Grasping by two fingertips plays a distinctive role in its performance related to robotic hand-environment interaction. A mathematical model including the dynamic equation has been derived based on the Lagrange technique. The coupling between two fingers and the fingertip contacts with unknown grasped objects has been presented in this model. The performance of the derived model is confirmed when a designed based model controller is implemented in Simulink. A computed torque controller of six PD controllers has been implemented to control the rotation of joints. The impedance controller is applied to operate as the outer loop of the overall control system. This controller allowed the regulation of the fingertip contact forces without overshoot response, which is essential for safe grasping, especially in holding fragile objects. Besides this, the impedance gains have been obtained using a genetic algorithm with a new behavior of improving the response of the position and velocity errors. The applied genetic algorithm method has minimized the position error and the velocity error while keeping the operation of the overall control system. The robot finger has been ordered to follow a specific joint path and fingertip position grasping; the results of simulations have achieved a typical accomplishment of trajectory tracking. Finally, the overall controllers have shown a perfect rejection of disturbances in terms of fingertip contact force. As a future work, it is recommended to apply the proposed controllers of this study to mobile manipulator for grasping and manipulation objects.
\nLet
\n\n\n
and
\nThen
\nThe partial derivatives of \n
The matrices’ elements in Eq. (28) are
\nThere may not be a precise background to the first discovery and application of phase change materials (PCMs). Perhaps, from the earliest days where human has acquired the intellect, he has realized the existence of these substances or, maybe, has used them without recognizing their nature. Throughout science and technology evolution, more precisely, since the heat capacity of materials and sensible or latent heats have been known, their ability to store and release thermal energy has also been considered. However, A. T. Waterman submitted the first report of discovery in the early 1900s. In recent years, scientists have paid particular attention to these materials, and their commercialization began from those years.
Perhaps the main reason for this attention was the problems caused by energy mismanagement and improper use of it. Today, inadequate energy management, especially fossil fuels, has caused many environmental and economic problems. Therefore, the necessity of efficient energy demand as well as development of renewable energies and energy storage systems is highly significant. One of the important topics in this field is the design of special energy storage equipment to other types. Energy storage not only reduces the discrepancy between energy supply and demand but also indirectly improves the performance of energy generation systems as well as plays a vital role in saving of energy by converting it into other reliable forms. Hence, this matter saves high-quality fuels and reduces energy wastes [1, 2, 3].
Energy storage is one of the important parts of renewable energies. Energy can be stored in several ways such as mechanical (e.g., compressed air, flywheel, etc.), electrical (e.g., double-layer capacitors), electrochemical (e.g., batteries), chemical (e.g., fuels), and thermal energy storages [4].
Among several methods of energy storage, thermal energy storage (TES) is very crucial due to its advantages. TES is accomplished by changing the internal energy of materials, such as sensible heat, chemical heat, latent heat, or a combination of them.
In sensible heat storage (SHS) systems, heat can be stored by increasing the temperature of a material. Hence, this system exploits both the temperature changes and the heat capacity of the material to store energy. The amount of heat stored in this system depends on the specific heat, temperature differences, and amount of material; thus it requires a large amount of materials, whereas Latent heat storage (LHS) is generally based on the amount of heat absorbed or released during the phase transformation of a material. Lastly, In the chemical heat storage (CHS), heat is stored by enthalpy change of a chemical reaction.
Among the aforementioned heat storage systems, the LHS is particularly noteworthy. One of the special reasons is its ability to store large amount of energy at an isothermal process [5, 6, 7].
Any high-performance LHS system should contain at least one of the following terms:
Appropriate PCM with optimum melting temperature range
Desirable and sufficient surface area proportional to the amount of heat exchange
Optimal capacity compatible with PCM
Phase change materials perform energy storage in LHS method. In this case, a material during the phase change absorbs thermal energy from surrounding to change its state, and in the reverse process, the stored energy is released to the surrounding. PCMs initially behave likewise to other conventional materials as the temperature increases, but energy is absorbed when the material receives heat at higher temperatures and close to the phase transformation. Unlike conventional materials, in PCMs absorption or release of thermal energy is performed at a constant temperature. A PCM normally absorbs and releases thermal energy 5–14 times more than other storage materials such as water or rock [8, 9].
PCMs can store thermal energy in one of the following phase transformation methods: solid-solid, solid-liquid, solid-gas, and liquid-gas. In the solid-solid phase change, a certain solid material absorbs heat by changing a crystalline, semicrystalline, or amorphous structure to another solid structure and vice versa [10]. This type of phase change, usually called phase transitions, generally has less latent heat and smaller volume change comparing to the other types. Recently, this type of PCM has been used in nonvolatile memories [11].
Solid-liquid phase change is a common type of commercial PCMs. This type of PCM absorbs thermal energy to change its crystalline molecular arrangement to a disordered one when the temperature reaches the melting point. Unlike solid-solid, solid-liquid PCMs contain higher latent heat and sensible volumetric change. Solid-gas and liquid-gas phase changes contain higher latent heat, but their phase changes are associated with large volumetric changes, which cause many problems in TES systems [8]. Although the latent heat of solid-liquid is less than liquid-gas, their volumetric change is much lower (about 10% or less). Therefore, employing PCMs based on solid-liquid phase change in TES systems would be more economically feasible.
The overall classification of energy storage systems as well as phase change materials is given in Figure 1.
Overview of energy storage and classification of phase change materials.
As mentioned in the previous section, despite the high thermal energy absorption capacity, PCMs in liquid-gas and solid-gas transitions have extremely high volume changes. On the other hand, solid-solid PCMs also have a lower thermal energy storage capacity. Therefore, the abovementioned PCMs, with the exception of specific cases, have not received much attention to commercialization. Currently, the most common type of transition that has been mass-marketed is solid-liquid PCMs. The classification of phase change materials is schematically given in Figure 1. Solid-liquid PCMs are generally classified as three general organics, inorganic, and eutectics [12, 13]. However, in some references they are classified into two major organics and inorganics.
Inorganic PCMs mainly have high capacity for thermal energy storage (about twice as much as organic PCMs) as well as have higher thermal conductivity. They are often classified as salt hydrates and metals.
Salt hydrates are the most important group of inorganic PCMs, which is widely employed for the latent heat energy storage systems. Salt hydrates are described as a mixture of inorganic salts and water (AB × nH2O). The phase change in salt hydrates actually involves the loss of all or plenty of their water, which is roughly equivalent to the thermodynamic process of melting in other materials.
At the phase transition, the hydrate crystals are subdivided into anhydrous (or less aqueous) salt and water. Although salt hydrates have several advantages, some deficiencies make restrictions in their application. One of these problems is incongruent melting behavior of salt hydrates. In this problem the released water from dehydration process is not sufficient for the complete dissolution of the salts. In this case, the salts precipitate and as a result phase separation occurs. In order to prevent this problem, an additional material such as thickener agent is added to salt hydrates. Another major problem with salt hydrates is the supercooling phenomenon. In this phenomenon, when crystallization process occurs, the nucleus formation is delayed; therefore, even at temperatures below freezing, the material remains liquid [7, 11, 14].
Overall, the most attractive properties of salt hydrate are (i) high alloy latent temperature, (ii) relatively high thermal conductivity (almost two to five times more than paraffin), and (iii) small volume changes in melting. They are also very low emitting and toxic, adaptable to plastic packaging, and cheap enough to use [15].
Metalsare another part of the inorganic PCMs. Perhaps the most prominent advantages of metals are their high thermal conductivity and high mechanical properties. Metals are available over a wide range of melting temperatures. They are also used as high-temperature PCMs.
Some metals such as indium, cesium, gallium, etc. are used for low-temperature PCMs, while others such as Zn, Mg, Al, etc. are used for high temperatures. Some metal alloys with high melting points (in the range of 400–1000°C) have been used for extremely high temperature systems. These metal alloys as high-temperature PCMs can be used in the field of solar power systems [16, 17]. They can also be used in industries that require temperature regulation in furnaces or reactors with high operating temperatures.
Perhaps the most important fragment is the organic PCMs. Organic PCMs show no change in performance or structure (e.g., phase separation) over numerous phase change cycles. In addition, supercooling phenomena cannot be observed in organic PCMs. The classification of organic PCMs is unique. This division is mainly based on their application contexts. In general, they are classified into two major paraffin and non-paraffin sections.
Paraffins are the most common PCMs. Since this book is about paraffin, to avoid duplication, this section will briefly discuss the chemistry (structure and properties) of paraffin, but their ability as phase change materials will be reviewed in detail.
Non-paraffinic organic PCMs are known to be the most widely used families. In addition to their different properties compared to paraffins, they have very similar properties to each other. Researchers have used various types of ether, fatty acid, alcohol, and glycol as thermal energy storage materials. These materials are generally flammable and less resistant to oxidation [18, 19, 20].
Although non-paraffin organic PCMs have high latent heat capacity, they have weaknesses such as flammability, low thermal conductivity, low combustion temperatures, and transient toxicity. The most important non-paraffinic PCMs are fatty acids, glycols, polyalcohols, and sugar alcohols.
Fatty acids [CH3(CH2)2nCOOH] also have high latent heat. They can be used in combination with paraffin. Fatty acids exhibit high stability to deformation and phase separations for many cycles and also crystallize without supercooling. Their main disadvantages are their costs. They are 2–2.5 times more expensive than technical grade paraffins. Unlike paraffins, fatty acids are of animal or plant origin. Their properties are similar to those of paraffins, but the melting process is slower. On the other hand, they are moderately corrosive as well as generally odorous [21].
A eutectic contains at least two types of phase change materials. Eutectics have exceptional properties. In eutectics, the melting-solidification temperatures are generally lower than the constituents and do not separate into the components through the phase change. Therefore, phase separation and supercooling phenomena are not observed in these materials.
Eutectics typically have a high thermal cycle than salt hydrates. Inorganic-inorganic eutectics are the most common type of them. However, in recent studies, organic-inorganic and organic-organic varieties have received more attention. The major problem of eutectics is their commercialization. Their cost is usually two to three times higher than commercial PCMs [22, 23].
Some of the above PCMs and their thermal properties, which are competitive with paraffins in terms of latent heat capacity, are summarized in Table 1.
Type of PCMs | Materials | Melting point (°C) | Latent heat (kJ/kg) | Density* (kg/m3) | Thermal conductivity (W/mK)** | Ref. | |
---|---|---|---|---|---|---|---|
Inorganic salt hydrates | LiClO3·3H2O | 8 | 253 | 1720 | [24, 25] | ||
K2HPO4·6H2O | 14 | 109 | [24] | ||||
Mn(NO3)2·6H2O | 25.8 | 126 | 1600 | [14, 25] | |||
CaCl2·6H2O | 29.8 | 191 | 1802 | 1.08 | [24, 25] | ||
Na2CO3·10H2O | 32–34 | 246–267 | [14, 24] | ||||
Na2SO4·10H2O | 32.4 | 248, 254 | 1490 | 0.544 | [14, 26] | ||
Na2HPO4·12H2O | 34–35 | 280 | 1522 | 0.514 | [15, 26] | ||
FeCl3·6H2O | 36–37 | 200, 226 | 1820 | [25, 26] | |||
Na2S2O3·5H2O | 48–49 | 200, 220 | 1600 | 1.46 | [15, 26] | ||
CH3COONa·3H2O | 58 | 226, 265 | 1450 | 1.97 | [15, 26] | ||
Non-paraffinic organic PCMs | Fatty acids | Formic acid | 8.3 | 247 | 1220 | — | [1, 25] |
n-Octanoic acid | 16 | 149 | 910 | 0.148 | [21, 27] | ||
Lauric acid | 43.6 | 184.4 | 867 | [21, 25] | |||
Palmitic acid | 61.3 | 198 | 989 | 0.162 | [21, 27] | ||
Stearic acid | 66.8 | 259 | 965 | 0.172 | [21, 25] | ||
Polyalcohols | Glycerin | 18 | 199 | 1250 | 0.285 | [1, 25] | |
PEG E600 | 22 | 127.2 | 1126 | 0.189 | [27] | ||
PEG E6000 | 66 | 190 | 1212 | [27] | |||
Xylitol | 95 | 236 | 1520 | 0.40 | [28] | ||
Erythritol | 119 | 338 | 1361 | 0.38 | [28] | ||
Others | 2-Pentadecanone | 39 | 241 | [1, 25] | |||
4-Heptadekanon | 41 | 197 | [1, 25] | ||||
D-Lactic acid | 52–54 | 126, 185 | 1220 | [1, 25] | |||
Eutectics | O-O, O-I, I-I *** | CaCl2·6H2O + MgCl2·6H2O | 25 | 127 | 1590 | [27] | |
Mg(NO3)2·6H2O + MgCl2·6H2O | 59 | 144 | 1630 | 0.51 | [27] | ||
Trimethylolethane + urea | 29.8 | 218 | [21] | ||||
CH3COONa·3H2O + Urea (60:40) | 31 | 226 | [27] | ||||
Metals | Mg-Zn (72:28) | 342 | 155 | 2850 | 67 | [16, 17] | |
Al-Mg-Zn (60:34:6) | 450 | 329 | 2380 | [16, 17] | |||
Al-Cu (82:18) | 550 | 318 | 3170 | [16, 17] | |||
Al-Si (87.8:12.2) | 580 | 499 | 2620 | [16, 17] |
Thermophysical properties of some common PCMs with high latent heat.
At 20°C.
Just above melting point (liquid phase).
Inorganic-inorganic (I-I), organic-inorganic (O-I), and organic-organic (O-O).
Paraffin is usually a mixture of straight-chain n-alkanes with the general formula CH3-(CH2)n-CH3. However, in some cases, paraffin is used as another name for alkanes. Gulfam R. et al. in their article have classified paraffins based on the number of carbon atoms as well as their physical states. According to this classification, at room temperature, 1–4 numbers of carbons refer to pure alkanes in a gas phase, 5–17 carbons are liquid paraffins, and more than 17 is known as solid waxes. These waxy solids refer to a mixture of saturated hydrocarbons such as linear, iso, high branched, and cycloalkanes [29]. Generally, paraffin-based PCMs are known as waxy solid paraffins. Commercial paraffins contain mixture of isomers, and therefore, they have a range of melting temperatures.
Paraffins typically have high latent heat capacity. If the length of the chain increases, the melting ranges of waxes also increase, while the latent heat capacity of melting is not subject to any particular order (Table 2).
Materials | Melting point (°C) | Latent heat (kJ/kg) | Density* (kg/m3) | Thermal conductivity** (W/mK) |
---|---|---|---|---|
n-Tetradecane (C14) | 6 | 228–230 | 763 | 0.14 |
n-Pentadecane (C15) | 10 | 205 | 770 | 0.2 |
n-Hexadecane (C16) | 18 | 237 | 770 | 0.2 |
n-Heptadecane (C17) | 22 | 213 | 760 | 0145 |
n-Octadecane (C18) | 28 | 245 | 865 | 0.148 |
n-Nonadecane (C19) | 32 | 222 | 830 | 0.22 |
n-Eicosane (C20) | 37 | 246 | ||
n-Henicosane (C21) | 40 | 200, 213 | 778 | |
n-Docosane (C22) | 44.5 | 249 | 880 | 0.2 |
n-Tricosane (C23) | 47.5 | 232 | ||
n-Tetracosane (C24) | 52 | 255 | ||
n-Pentacosane (C25) | 54 | 238 | ||
n-Hexacosane (C26) | 56.5 | 256 | ||
n-Heptacosane (C27) | 59 | 236 | ||
n-Octacosane (C28) | 64.5 | 253 | ||
n-Nonacosane (C29) | 65 | 240 | ||
n-Triacontane (C30) | 66 | 251 | ||
n-Hentriacontane (C31) | 67 | 242 | ||
n-Dotriacontane (C32) | 69 | 170 | ||
n-Triatriacontane (C33) | 71 | 268 | 880 | 0.2 |
Paraffin C16-C18 | 20–22 | 152 | ||
Paraffin C13-C24 | 22–24 | 189 | 900 | 0.21 |
RT 35 HC | 35 | 240 | 880 | 0.2 |
Paraffin C16-C28 | 42–44 | 189 | 910 | |
Paraffin C20-C33 | 48–50 | 189 | 912 | |
Paraffin C22-C45 | 58–60 | 189 | 920 | 0.2 |
Paraffin C21-C50 | 66–68 | 189 | 930 | |
RT 70 HC | 69–71 | 260 | 880 | 0.2 |
Paraffin natural wax 811 | 82–86 | 85 | 0.72 (solid) | |
Paraffin natural wax 106 | 101–108 | 80 | 0.65 (solid) |
In general, paraffin waxes are safe, reliable, inexpensive, and non-irritating substances, relatively obtained in a wide range of temperatures. As far as economic issues are concerned, most technical grade waxes can be used as PCMs in latent heat storage systems. From the chemical point of view, paraffin waxes are inactive and stable. They exhibit moderate volume changes (10–20%) during melting but have low vapor pressure.
The paraffin-based PCMs usually have high stability for very long crystallization-melting cycles. Table 2 illustrates the thermal properties of some paraffin waxes.
Besides the favorable properties, paraffins also show some undesirable properties such as low thermal conductivity, low melting temperatures, and moderate-high flammability. Some of these disadvantages especially thermal conductivity and flammability can be partially eliminated with the help of additives or paraffin composites.
Measures must be taken to make the solid-liquid PCMs usable. For this purpose, there are several methods for stabilizing the shapes of paraffinic PCMs. Two main methods of them are discussed below.
Encapsulation is generally a worthy method to protect and prevent leakage of PCMs in the liquid state. The capsules consist of two parts, the shell and the core. The core part contains PCMs, whereas the shell part is usually composed of polymeric materials with improved mechanical and thermal properties. The shell part plays the role of protection, heat transfer, and sometimes preventing the release of toxic materials into the environment. In these cases, the shell must have appropriate thermal conductivity. Polymeric shells are also commonly used in encapsulating PPCMs. The choice of core part depends on its application field. The encapsulation of PPCMs is classified into three major parts: bulk or macroencapsulation, microencapsulation, and nano-encapsulation.
Macroencapsulation is one of the simplest ways to encapsulate paraffins. This method has a lower cost than other methods. These products are used in transportation, buildings, solar energy storage systems, and heat exchangers. Sometimes metals are also used as shell materials [30].
In order to increase the efficiency of heat transfer in these types of capsules, either the size of the capsules should be appropriately selected or suitable modifiers should be used. In general, the smaller the diameter of spherical capsules or cylinders, the better the heat transfer. In some cases, metal foams are used to improve the heat transfer properties of paraffin. Aluminum and copper open-cell foams are among the most studied, whereas, in other cases metal oxides, metals and graphite are used [30, 31].
There are various forms of macroencapsulation, such as ball shape, spherical shape, cylindrical, flat sheets, tubular, etc. [31]. Cylindrical tubes are one of the famous forms of macroencapsulated PPCMs. This type of encapsulation is most commonly used in buildings or in solar energy storage systems.
Most of the research carried out on macroencapsulated PPCMs has been focused on improving their thermal conductivity. In one of these studies, different metal oxide nanoparticles such as aluminum oxide, titanium oxide, silicon oxide, and zinc oxide were used to improve the thermal conductivity of paraffin. The results show that titanium oxide performs better under the same conditions than the other oxides [32]. In a similar study, copper oxide nanoparticles were used to improve thermal conductivity and performance of paraffin in solar energy storage systems [33]. In some studies, graphite flakes and expanded graphite have also been used as improving agent for heat conductivity [31].
Hong et al. have used polyethylene terephthalate pipes as a shell for paraffin. In this macroencapsulated system, introduced as cylinder modules, float stone has been added to paraffin as an enhancer of thermal conductivity. In this study, the effect of various parameters such as pipe diameter on heat transfer is investigated, and the results of experimental section are compared with modeling [34].
D. Etansova et al. studied numerical computation and heat transfer modeling of paraffin-embedded stainless steel macroencapsulates for use in solar energy storage systems. In this study, the effect of geometric size and shape on heat transfer was investigated [35].
Microencapsulation of PCMs is another suitable way to improve efficiency and increase thermal conductivity. The size of the microencapsulates usually ranges from 1 μm to 1 mm. Microencapsulation of paraffins is a relatively difficult process, but it performs better than macroencapsulates. This is due to increased contact surface area, shorter discharge and loading times, and improved thermal conductivity. Different materials are used for the shell part of the microencapsulates.
In general, there are two major physical and chemical methods for microencapsulation. The most important physical methods are fluidized bed, spray dryer, centrifuge extruder, and similar processes. However, chemical methods are often based on polymerization. The most important techniques include in situ suspension and emulsion polymerization, interfacial condensation polymerization, and sol-gel method. The latter is sometimes known as the physicochemical method [12, 29].
In the suspension or emulsion polymerization method, the insoluble paraffin is first emulsified or suspended in a polar medium, which is predominantly aqueous phase, by means of high-speed stirring. Surfactants are used to stabilize the particles. Then, lipophilic monomers are added to the medium, and the conditions are prepared for polymerization. This polymer, which is insoluble in both aqueous and paraffin phases, is formed on the outer surface of paraffin particles and finally, after polymerization, encapsulates the paraffin as a shell. The size of these capsules depends on the size of emulsion or suspension of paraffin droplets. Sometimes certain additives are added to the medium to improve some of the polymer properties. For instance, in some studies, polyvinyl alcohol (PVA) has been added to the medium with methyl-methacrylate monomer, which is known as one of the most important shell materials. As a result, paraffin has been encapsulated by PVA modified polymethyl methacrylate (PMMA). Adding this modifier forms a smooth surface of the microencapsulates [36, 37].
In the interfacial method, soluble monomers in the organic phase with other monomers in the aqueous phase at the droplet interface form a polymer that precipitates on the outer layer of the organic phase.
The sol-gel method is a multi-step procedure. In this method, firstly, an organosilicon compound such as tetraethoxysilane (TEOS) is hydrolyzed in an acidic medium at low pH. The prepared homogenous solution is known as the sol part. Then, the paraffin emulsion is prepared in an aqueous medium and stabilized by special emulsifiers. Actually, these emulsifiers are the first layer of the shell. Subsequently, the sol solution is slowly added to the aqueous phase containing paraffin. The silicon compounds containing OH groups (silanols) form hydrogen bonding with polar side of emulsifiers, and finally the condensation process is carried out on the first layer interface. As a result, paraffin microencapsulates with an inorganic material that is often silica. Silica is one of the significant materials used as a shell for micro and nano-encapsulation. Silica has high thermal conductivity and on the other hand has better mechanical properties than some polymers [38, 39, 40, 41].
As mentioned, most of the materials used to microencapsulation are polymers. The main polymers used as shell materials are polymethyl methacrylate [42], polystyrene [43], urea-formaldehyde [44], urea-melamine-formaldehyde [45], polyaniline [46], etc. However, in many cases, these polymers are used in modified form. For example, polymethyl methacrylate modified with polyvinyl alcohol or with other methacrylates [36, 37], polystyrene copolymers [47], and melamine modified-formaldehyde with methanol [48] can be considered. Table 3 shows the most common polymers used as shell materials.
Core material PPCM | Shell material | Encapsulation method | Particle size (μm) | Recommended application | Ref |
---|---|---|---|---|---|
n-Nonadecane | Polymethyl methacrylate | Emulsion | ~ 8 | Smart building and textiles | [42] |
n-Heptadecane | Polystyrene | Emulsion | <2 | General fields | [43] |
Commercial paraffin wax | Polystyrene-co-PMMA | Suspension | ~ 20 | [50] | |
Commercial RT21 | PMMA | Suspension | 20–40 | [36] | |
Commercial RT21 | PMMA modified with PVA | Emulsion | 15 | Building | [37] |
Commercial paraffin wax | Polyaniline | Emulsion | <1 | [46] | |
Commercial paraffin wax | Urea-formaldehyde | In situ | ~ 20 | [44] | |
n-Octadecane, n-nonadecane | Urea-melamine-formaldehyde | In situ | 0.3-0.6 | [45] | |
Commercial paraffin wax | Methanol-melamine-formaldehyde | In situ | 10–30 | Building | [48] |
Commercial paraffin wax | Silica | Sol-gel | 4–10 | Textile | [38] |
Commercial paraffin wax | Silica | Sol-gel | 0.2–0.5 | [39] | |
n-Octadecane | Silica | Sol-gel | 7–16 | [40] | |
n-Pentadecane | Silica | Sol-gel | 4–8 | [41] |
Common materials for microencapsulation of PPCMs.
In addition to the aforementioned microencapsulation approaches, which mainly form polymeric materials as shells, other materials have been also recommended. For example, Singh and colleagues have used silver metal as a shell for paraffin microencapsulates. They first emulsified paraffin into small particles in water and then converted silver salts to metallic silver via an in situ reduction reaction. The average particle size of 329 μm has been reported, and the thermal properties of paraffin have been investigated using DSC and TGA. This type of metal shell microencapsulates has been suggested for use in microelectronics heat management systems [49].
There are several techniques to study the properties of micro and nano-encapsulates. In all studies, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) have been used to determine the thermal properties of PPCMs, such as enthalpy of fusion, melting temperature, weight loss, degradation, etc. Various methods such as XRD, FTIR, and 12C NMR have been used to study the structure and chemical composition of PPCMs. The morphology and diameters of the microcapsules have often been studied by scanning electron microscopy (SEM) and particle size analyzer.
The latter technique is used to study the influence of different variables on the diameter of the microcapsules. One of these variables is the effect of stirring speed on emulsification of paraffin. The results of some studies show that higher stirring speed of emulsification process leads to decrease of the mean size of paraffin droplets [48].
Along with studies on the type of microcapsules, many studies have been conducted to improve thermal conductivity and mechanical properties of microencapsulates. Part of these studies has been dedicated to the effect of graphene and graphene oxide on the improvement of thermal conductivity [51]. L. Zhang et al. investigated the effect of graphene oxide on improving the mechanical properties and leakage protection as well as improving the thermal conductivity of melamine-formaldehyde as shell materials of PPCM microencapsulates [52]. In another part of studies, metals and metal oxides have been used. For example, 10 and 20 wt% of nanomagnetite (Fe3O4) with particle size from 40 to 75 nm increase the thermal conductivity by 48 and 60%, respectively [53]. Also, addition of TiO2 and Al2O3 nanoparticles in a mass fraction of 5% with respect to PPCM at the size range of 30–60 nm increases the thermal conductivity by 40 and 65%, respectively [54].
Nano-encapsulation of PPCM is very similar to the microencapsulation process. However, these types of encapsulation specific techniques, such as ultrasonic, are used to adjust the size of the paraffin droplets to less than 1 micron. In the next step, using the chemical methods mentioned in the microencapsulation method, the shell formation is performed. The most common method for nano-encapsulation is the emulsion polymerization method. However, although limited, interfacial and sol-gel methods have also been reported.
In recent years, research on polymeric matrix-based shape-stable PCMs has gained great importance. Among these types of phase change materials, the paraffin-polymer composite is particularly attractive. The combination of paraffin and polymers as new PCMs with a unique controllable structure can be widely used. This compound remains solid at paraffin melting point and even above without any softening, which is why this type of PCM is called shape-stable. These materials are well formed and have high-energy absorption capacity; hence they can be widely used as stable PCMs with specific properties. On the other hand, some problems such as high cost and difficulty of encapsulating processes could be resolved. Despite these advantages, some common disadvantages such as low thermal stability, low thermal conductivity, and relatively high flammability can restrict their application, particularly in building materials. For this reason, further studies are required to eliminate these disadvantages and improve the properties of these materials. A large part of research is relevant to increase or improve their thermal conductivity, flame retardation, and thermophysical and mechanical properties. Suitable additives are proposed to improve these properties [55, 56].
In some articles, a simple method involves mixing-melting of polyethylene and paraffin, consequently cooling the composite, or using a simple twin extruder to prepare a shape-stable PCM has been reported [57, 58]. When this compound contains sufficient polymer, a homogeneous mixture remains solid at temperatures above the melting point of paraffin and below the polymer melting point. During the preparation of these composites, no chemical reaction or chemical bonds are formed between the polymers and paraffin; therefore these types of compounds are considered as physical mixtures. Shape-stable PPCMs can be used in all previously described areas. Due to the thermoplastic properties of these composites, it is possible to melt and crystalize them for many cycle numbers. Shape-stable PPCMs have several advantages over other PCMs. They are also nontoxic and do not require high-energy consumption during production process.
Inaba and Tu [59] developed a new type of shape-stable PPCM and determined their thermophysical properties. These materials can be used without encapsulation. Feldman et al. [60] prepared plates of shape-stable PCM and determined their high thermal energy storage capacity when used in small chambers. In this type of polymer-based plates, fatty acids are used as PCMs that absorb or releases large amounts of heat during melting and solidification, without altering the composition of the shape-stable PCM. The same researchers determined the role of polymer-PCM sheets in stabilizing the shape and size of the plates when PCM was liquefied. The composition of paraffin and high-density polyethylene (HDPE) has been studied by Lee and Choi [61] and has been introduced as a shape-stable energy storage material. In this study, the amount of energy stored by the mentioned composites is also studied. They also studied the morphology of the high-density polyethylene crystal lattice (HDPE) and its effect on paraffin through scanning electron microscopy and optical microscopy (OM) analysis. On the other hand, they also reported of high thermal energy storage capacity of the prepared paraffin/HDPE-based shape-stable PCMs. Hong and Xin-Shi [62] synthesized polyethylene-paraffin as a shape-stable PCM and characterized its morphology and structure by scanning electron microscopy and its latent heat of melting by differential scanning calorimetry. In this study, a composition consisting of 75% paraffin as a cheap, effective, easy-to-prepare, low-temperature shape-stable PPCM is recommended. In another study, Xiao et al. [63] prepared a shape-stable PCM based on the composition of paraffin with a thermoplastic elastomer (styrene butadiene rubber) and determined its thermal properties. The obtained results show that the stable mixture has the phase changing property and the amount of latent heat of melting stored in this compound is estimated to be 80% of pure paraffin. In another part of this study, the thermal conductivity of PCMs was significantly increased by using graphite.
Despite the above benefits, some disadvantages of shape-stable PPCMs are also reported. One of the major problems is the softening and paraffin leakage phenomenon at elevated temperatures. Seiler partly resolved this problem by adding a different ratio of silica and copolymers to the polyethylene-paraffin composition [64]. Another problem is the low thermal conductivity of the polyethylene-paraffin compound. A lot of research has been conducted to increase this property. A. Sari [65] prepared two types of paraffin with different melting temperatures (42–44°C and 56–58°C) and combined each with HDPE as phase modifier. By addition of 3% expanded graphite, the thermal conductivity of composites increased by 14 and 24%, respectively. Zhang et al. [66] developed new PCMS based on graphite and paraffin with high thermal energy storage capacity and high thermal conductivity. Zhang and Ding et al. [67] have used various additives such as diatomite, Wollastonite, organic modified bentonite, calcium carbonate, and graphite to improve the thermal conductivity of shape-stable PCMs.
It should be noted that metal particles and metal oxides due to their higher thermal conductivity are widely used to improve this property of PCMs. One of the materials that has received more attention in recent years is alumina. Aluminum oxide nanoparticles were added to paraffin to increase its thermal conductivity in both liquid and solid states [57, 68]. This compound coupled with its high thermal conductivity is cheaper and more abundant than other metal oxides.
Another problem with shape-stable PPCMs is their flammability. The effect of various additives has been studied by scientists to eliminate this problem. One of the most effective of these substances is halogenated compounds, but they cause environmental pollution and also release toxic compounds while burning. Researchers have used hybrid and environmentally friendly materials to enhance the durability of flame retardant materials. They studied the effect of clay nanoparticles and organo-modified montmorillonite. Adding these materials not only increases their resistance to burning but also increases their mechanical and thermal properties [69, 70, 71]. In another study, Y. Cai et al. added paraffin, HDPE, and graphite, then added ammonium polyphosphate and zinc borate separately, and studied their resistance to burning. The results show that the addition of ammonium polyphosphate decreases flammability, while zinc borate increases the flammability risk [72]. One of the most interesting and harmless fire retardant compounds is metal hydroxides, especially aluminum hydroxide, magnesium hydroxide, or their combination [73, 74, 75].
Some researchers have used other advanced materials as supporting materials to prepare shape-stable PPCMs instead of using the polymer matrix [76, 77, 78]. Rawi et al. used acid-treated multi-walled carbon nanotubes (A-CNT). They reported that adding 5% by weight A-CNT to paraffin decreases 25% of the latent heat while increasing heat conductivity up to 84% [79]. Y. Wan et al. used pinecone biochar as the supporting matrix for PCMs. They prepared shape-stable PCM materials at different ratios and studied the leakage behavior. The optimal ratio is suggested as 60% of the PCM. For the above ratio, no PCM leakage was observed after the melting temperature. The results showed that the thermal conductivity of the same ratio shape-stable PCM increased by 44% compared to the pure PCM [80].
PCMs are available in a wide range of desired temperature ranges. Obviously, a PCM may not have all the properties required to store heat energy as an ideal material. Therefore, it would be more appropriate to use these materials in combination with either other PCMs or various additives to achieve the required features. However, as latent heat storage materials, while using PCMs, the thermodynamic, kinetic, and chemical properties as well as the economic and availability issues of them must be taken into account. Employed PCMs must have the optimum phase change temperature. On the other hand, the higher the latent heat of the material, the lower its physical size. High thermal conductivity also helps to save and release energy. From the physical and kinetic point of view, the phase stability of PCMs during melting and crystallization contributes to optimum thermal energy storage. Their high density also enables high storage at smaller material sizes. During phase change, smaller volume changes and lower vapor pressures are appropriate for continuous applications.
H. Nazir et al. in their review article [12] have explained the criteria for selection of PCMs as a pyramid. In this pyramid, at the bottom, known as the fundamentals, there are several items such as cost, regularity compliance, and safety. In the next section, the thermophysical properties such as energy storage capacity and runtime are discussed. In the upper section, reliability and operating environment consist of degradation, cycle life, shelf life, and thermal limits are reflected. Finally, at the top section of pyramid, user perception and convenience are located. These criteria help us to find a proper PCM for certain application fields.
These criteria may also be extended to paraffinic PCMs. Nowadays, paraffinic PCMs (PPCMs) are widely used as thermal energy storage materials, including solar energy storage systems, food industries, medical fields, electrical equipment protection, vehicles, buildings, automotive industries, etc. [24, 29, 81, 82, 83, 84, 85].
Generally, application fields of PPCMs can be considered in two main sections: thermal protection and energy storage purposes. The major difference between these two areas of application is in thermal conductivity of the PPCMs.
Protection and transportation of temperature-sensitive materials is one the mentioned area. Sometimes a certain temperature is required to transport sensitive medicines, medical equipment, food, etc. In all cases, using of PPCMs would be appropriate as they can regulate and stabilize the temperature over a given range. Similarly, in sensitive electrical equipment, these materials are also essential to prevent the maximum operating temperature. On the other hand, they can be used to prevent possible engine damage at high temperatures [86, 87].
One of the studies related to these issues is the use of paraffin containing heavy alkanes to protect electronic devices against overheating. In this study, paraffin has been used as a protective coating for the resistor chip, and its effect on cooling of the devices has been investigated. Experimental results show that paraffin coating increases the relative duration of overheating by 50 to 150% over the temperature range of 110–140°C [88]. In another study, a mixture of paraffin and polypropylene has been used as an overheating protector in solar thermal collectors [89].
However, energy storage purposes are the most important part of PPCM application. In general, PCMs act as passive elements and therefore do not require any additional energy source. Most studies on the application of energy storage properties of PPCMs have been confined to buildings, textiles, and solar systems. In the following, building applications will be further attended.
One of the main drawbacks of lightweight building materials is their low thermal storage capacity, which results in extensive temperature fluctuations as a result of intense heating and cooling. Therefore, PPCMs have been used in buildings due to their ability to regulate and stabilize indoor temperatures at higher or lower outdoor temperatures [90].
Generally, PPCMs in buildings are used as thermal energy storage at daytime peak temperature, and they released the stored energy at night when temperatures are low. The result of this application is to set the comfort condition for a circadian period. This application minimizes the amount of energy consumed for cooling during the day and warming up at night.
In contrast, in order to stabilize the ambient conditions at low temperatures, some special PCMs are also used in air conditioner systems. In this case, cool air is stored during the night and released into the warm hours of the day.
Y. Cui et al. [91] in a review article categorized PPCM application methods based on their location of use such as PCMs in walls, floor heating systems, ceiling boards, air-based solar heating systems, free cooling systems (with ventilation systems), and PCM shutter (in windows). Both types of encapsulation and shape-stable PPCMs could be used in all of the above classification of building applications. Sometimes these materials can be added directly to concrete, gypsum, etc. [90, 92, 93, 94, 95].
In order to increase the performance of PPCMs in this application field, great deals of studies have also been done on improving their thermal conductivity. On the other hand, extensive research into safety issues has been done to reduce the flammability of PPCMs by adding flame retardants to these materials.
Overall, these studies cover the importance of using PPCMs in heating and cooling as well as indicate the general characteristics, advantages, and disadvantages of these materials used for thermal storage in buildings.
It is clear that at this time, where renewable energy is particularly important, the use of PPCMs is on the rise. As it has been mentioned, PPCMs have many application fields due to their advantages. For example, they can be used in the construction, pharmaceutical and medical industries, textiles, automobiles, solar power systems, transportation, thermal batteries, heat exchangers, and so on.
This chapter of the book has attempted to focus more on how to use paraffins. For this reason, two methods, namely, encapsulation and shape-constant, have been widely discussed. In addition, improving their weak properties such as thermal conductivity and flammability has also been studied. Depending on the benefits of paraffins, new applications are suggested every day. Extensive studies are underway on other new applications in recent years.
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",metaTitle:"Prior Publication Policy",metaDescription:"Prior Publication Policy",metaKeywords:null,canonicalURL:"/page/prior-publication-policy",contentRaw:'[{"type":"htmlEditorComponent","content":"A significant number of working papers, early drafts, and similar work in progress are openly shared online between members of the scientific community. It has become common to announce one’s own research on a personal website or a blog to gather comments and suggestions from other researchers. Such works and online postings are, indeed, published in the sense that they are made publicly available. However, this does not mean that if submitted for publication by IntechOpen they are not original works. We differentiate between reviewed and non-reviewed works when determining whether a work is original and has been published in a scholarly sense or not.
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\\n"}]'},components:[{type:"htmlEditorComponent",content:'A significant number of working papers, early drafts, and similar work in progress are openly shared online between members of the scientific community. It has become common to announce one’s own research on a personal website or a blog to gather comments and suggestions from other researchers. Such works and online postings are, indeed, published in the sense that they are made publicly available. However, this does not mean that if submitted for publication by IntechOpen they are not original works. We differentiate between reviewed and non-reviewed works when determining whether a work is original and has been published in a scholarly sense or not.
\n\nThe significance of Peer Review cannot be overstated when it comes to defining, in our terms, what constitutes a published scientific work. Peer Review is widely considered to be the cornerstone of modern publishing processes and the key value-adding contribution to a scholarly manuscript that a publisher can make.
\n\nOther than the issue of originality, research misconduct is another major issue that all publishers have to address. IntechOpen’s Retraction & Correction Policy and various publication ethics guidelines identify both redundant publication and (self)plagiarism to fall within the definition of research misconduct, thus constituting grounds for rejection or the issue of a Retraction if the work has already been published.
\n\nIn order to facilitate the tracking of a manuscript’s publishing history and its development from its earliest draft to the manuscript submitted, we encourage Authors to disclose any instances of a manuscript’s prior publication, whether it be through a conference presentation, a newspaper article, a working paper publicly available in a repository or a blog post.
\n\nA note to the Academic Editor containing detailed information about a submitted manuscript’s previous public availability is the preferred means of reporting prior publication. This helps us determine if there are any earlier versions of a manuscript that should be disclosed to our readers or if any of those earlier versions should be cited and listed in a manuscript’s references.
\n\nSome basic information about the editorial treatment of different varieties of prior publication is laid out below:
\n\n1. CONFERENCE PAPERS & PRESENTATIONS
\n\nGiven that conference papers and presentations generally pass through some sort of peer or editorial review, we consider them to be published in the accepted scholarly sense, particularly if they are published as a part of conference proceedings.
\n\nAll submitted manuscripts originating from a previously published conference paper must contain at least 50% of new original content to be accepted for review and considered for publication.
\n\nAuthors are required to report any links their manuscript might have with their earlier conference papers and presentations in a note to the Academic Editor, as well as in the manuscript itself. Additionally, Authors should obtain any necessary permissions from the publisher of their conference paper if copyright transfer occurred during the publishing process. Failure to do so may prevent Us from publishing an otherwise worthy work.
\n\n2. NEWSPAPER & MAGAZINE ARTICLES
\n\nNewspaper and magazine articles usually do not pass through any extensive peer or editorial review and we do not consider them to be published in the scholarly sense. Articles appearing in newspapers and magazines rarely possess the depth and structure characteristic of scholarly articles.
\n\nSubmitted manuscripts stemming from a previous newspaper or magazine article will be accepted for review and considered for publication. However, Authors are strongly advised to report any such publication in an accompanying note to the External Editor.
\n\nAs with the conference papers and presentations, Authors should obtain any necessary permissions from the newspaper or magazine that published the work, and indicate that they have done so in a note to the External Editor.
\n\n3. GREY LITERATURE
\n\nWhite papers, working papers, technical reports and all other forms of papers which fall within the scope of the ‘Luxembourg definition’ of grey literature do not pass through any extensive peer or editorial review and we do not consider them to be published in the scholarly sense.
\n\nAlthough such papers are regularly made publicly available via personal websites and institutional repositories, their general purpose is to gather comments and feedback from Authors’ colleagues in order to further improve a manuscript intended for future publication.
\n\nWhen submitting their work, Authors are required to disclose the existence of any publicly available earlier drafts in a note to the Academic Editor. In cases where earlier drafts of the submitted version of the manuscript are publicly available, any overlap between the versions will generally not be considered an instance of self-plagiarism.
\n\n4. SOCIAL MEDIA, BLOG & MESSAGE BOARD POSTINGS
\n\nWe feel that social media, blogs and message boards are generally used with the same intention as grey literature, to formulate ideas for a manuscript and gather early feedback from like-minded researchers in order to improve a particular piece of work before submitting it for publication. Therefore, we do not consider such internet postings to be publication in the scholarly sense.
\n\nNevertheless, Authors are encouraged to disclose the existence of any internet postings in which they outline and describe their research or posted passages of their manuscripts in a note to the Academic Editor. Please note that we will not strictly enforce this request in the same way that we would instructions we consider to be part of our conditions of acceptance for publication. We understand that it may be difficult to keep track of all one’s internet postings in which the researcher´s current work might be mentioned.
\n\nIn cases where there is any overlap between the Author´s submitted manuscript and related internet postings, we will generally not consider it to be an instance of self-plagiarism. This also holds true for any co-Author as well.
\n\nFor more information on this policy please contact permissions@intechopen.com.
\n\nPolicy last updated: 2017-03-20
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