Physical properties of springs.
\\n\\n
Released this past November, the list is based on data collected from the Web of Science and highlights some of the world’s most influential scientific minds by naming the researchers whose publications over the previous decade have included a high number of Highly Cited Papers placing them among the top 1% most-cited.
\\n\\nWe wish to congratulate all of the researchers named and especially our authors on this amazing accomplishment! We are happy and proud to share in their success!
Note: Edited in March 2021
\\n"}]',published:!0,mainMedia:null},components:[{type:"htmlEditorComponent",content:'IntechOpen is proud to announce that 191 of our authors have made the Clarivate™ Highly Cited Researchers List for 2020, ranking them among the top 1% most-cited.
\n\nThroughout the years, the list has named a total of 261 IntechOpen authors as Highly Cited. Of those researchers, 69 have been featured on the list multiple times.
\n\n\n\nReleased this past November, the list is based on data collected from the Web of Science and highlights some of the world’s most influential scientific minds by naming the researchers whose publications over the previous decade have included a high number of Highly Cited Papers placing them among the top 1% most-cited.
\n\nWe wish to congratulate all of the researchers named and especially our authors on this amazing accomplishment! We are happy and proud to share in their success!
Note: Edited in March 2021
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These results cover a large range of the problems that are frequently encountered in the motion planning of mobile robots both in theoretical methods and practical applications including obstacle avoidance methods, navigation and localization techniques, environmental modelling or map building methods, and vision signal processing etc. Different methods such as potential fields, reactive behaviours, neural-fuzzy based methods, motion control methods and so on are studied. Through this book and its references, the reader will definitely be able to get a thorough overview on the current research results for this specific topic in robotics. 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Interested readers will find in this book the topics of image compression, groundwater quality, establishing the downscaling and spatio-temporal scale conversion models of NDVI, modelling and optimization of 3T fractional nonlinear generalized magneto-thermoelastic multi-material, algebraic fractals in steganography, strain induced microstructures in metals and much more. The book will definitely be of interest to scientists dealing with fractal analysis, as well as biomedical engineers or IT engineers. I encourage you to view individual chapters.",isbn:"978-1-83962-483-4",printIsbn:"978-1-83962-482-7",pdfIsbn:"978-1-83962-484-1",doi:"10.5772/intechopen.87695",price:119,priceEur:129,priceUsd:155,slug:"fractal-analysis-selected-examples",numberOfPages:128,isOpenForSubmission:!1,hash:"f0c3d700a69d15b52ff8a59fe7e99062",bookSignature:"Robert Koprowski",publishedDate:"September 9th 2020",coverURL:"https://cdn.intechopen.com/books/images_new/9886.jpg",keywords:null,numberOfDownloads:1093,numberOfWosCitations:0,numberOfCrossrefCitations:0,numberOfDimensionsCitations:0,numberOfTotalCitations:0,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"October 1st 2019",dateEndSecondStepPublish:"March 3rd 2020",dateEndThirdStepPublish:"May 2nd 2020",dateEndFourthStepPublish:"July 21st 2020",dateEndFifthStepPublish:"September 19th 2020",remainingDaysToSecondStep:"a year",secondStepPassed:!0,currentStepOfPublishingProcess:5,editedByType:"Edited by",kuFlag:!1,biosketch:null,coeditorOneBiosketch:null,coeditorTwoBiosketch:null,coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:[{id:"50150",title:"Prof.",name:"Robert",middleName:null,surname:"Koprowski",slug:"robert-koprowski",fullName:"Robert Koprowski",profilePictureURL:"https://mts.intechopen.com/storage/users/50150/images/system/50150.jpg",biography:"Robert Koprowski, MD (1997), PhD (2003), Habilitation (2015), is an employee of the University of Silesia in Poland, Institute of Computer Science, Department of Biomedical Computer Systems. For 20 years he has studied the analysis and processing of biomedical images with particular emphasis on the full automation of measurement for a large inter-individual variability of patients. He is the author of dozens of papers with the impact factor (IF) and more than a hundred other papers, as well as the author or co-author of six books. Additionally, he is the author of several national and international patents in the field of biomedical devices and imaging. Since 2011, he has been a reviewer of grants and projects (including EU projects) in the field of biomedical engineering.",institutionString:"University of Silesia",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"1",totalChapterViews:"0",totalEditedBooks:"2",institution:{name:"University of Silesia",institutionURL:null,country:{name:"Poland"}}}],coeditorOne:null,coeditorTwo:null,coeditorThree:null,coeditorFour:null,coeditorFive:null,topics:[{id:"1407",title:"Applied Mathematics",slug:"numerical-analysis-and-scientific-computing-applied-mathematics"}],chapters:[{id:"72917",title:"Optimization of Fractal Image Compression",slug:"optimization-of-fractal-image-compression",totalDownloads:190,totalCrossrefCites:0,authors:[null]},{id:"72577",title:"Fractal Analysis for Time Series Datasets: A Case Study of Groundwater Quality",slug:"fractal-analysis-for-time-series-datasets-a-case-study-of-groundwater-quality",totalDownloads:172,totalCrossrefCites:0,authors:[null]},{id:"71255",title:"Establishing the Downscaling and Spatiotemporal Scale Conversion Models of NDVI Based on Fractal Methodology",slug:"establishing-the-downscaling-and-spatiotemporal-scale-conversion-models-of-ndvi-based-on-fractal-met",totalDownloads:207,totalCrossrefCites:0,authors:[null]},{id:"72883",title:"A New BEM for Modeling and Optimization of 3T Fractional Nonlinear Generalized Magneto-Thermoelastic Multi-Material ISMFGA Structures Subjected to Moving Heat Source",slug:"a-new-bem-for-modeling-and-optimization-of-3t-fractional-nonlinear-generalized-magneto-thermoelastic",totalDownloads:154,totalCrossrefCites:0,authors:[{id:"233766",title:"Prof.",name:"Mohamed Abdelsabour",surname:"Fahmy",slug:"mohamed-abdelsabour-fahmy",fullName:"Mohamed Abdelsabour Fahmy"}]},{id:"71839",title:"Using Algebraic Fractals in Steganography",slug:"using-algebraic-fractals-in-steganography",totalDownloads:178,totalCrossrefCites:0,authors:[null]},{id:"71305",title:"Fractal Analysis of Strain-Induced Microstructures in Metals",slug:"fractal-analysis-of-strain-induced-microstructures-in-metals",totalDownloads:195,totalCrossrefCites:0,authors:[null]}],productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"},personalPublishingAssistant:{id:"247865",firstName:"Jasna",lastName:"Bozic",middleName:null,title:"Ms.",imageUrl:"https://mts.intechopen.com/storage/users/247865/images/7225_n.jpg",email:"jasna.b@intechopen.com",biography:"As an Author Service Manager, my responsibilities include monitoring and facilitating all publishing activities for authors and editors. 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Therefore, the myoelectric prosthetic hand can be moved freely as intended by the user. However, the user cannot feel sensations when he/she touches an object using the prosthetic hand. Healthy person uses the tactile sense and temperature sense to check the state of the object that he/she touched. A myoelectric prosthetic hand cannot produce any sensations. Therefore, the user has to operate the prosthetic hand only based on visual information. Thus, the user needs to watch the object constantly. This is a burden to the user. To solve this problem, sensory feedback which provides sensation to the user has been studied. Sensory feedback systems for an upper limb prosthesis in the initial stage have been reported in [1]. Summary of studies involving sensory feedback in upper limb prosthetics is listed in [2].
\nA method of providing a sense of touch realized by vibration stimulation was proposed in [3], and a method of sensory feedback realized by the combination of vibration stimulation and electric stimulation was proposed in [4], respectively. On the other hand, Otsuka et al. [5] developed a device that perceives the temperature when an object was touched by a myoelectric prosthetic hand using a hot and cold pad. Morimitsu and Katsura [6] examined transfer of temperature sense using the Peltier element.
\nIn this study, two types of sensory feedback device were developed to enhance the quality of life (QOL) of myoelectric prosthetic hand users. First, a compact feedback device of force sense (hereinafter referred to as FFB device) with a safety mechanism was developed. The FFB device is mounted on the user’s upper arm, and when a prosthetic hand holds an object, a belt in the device is winded by a motor to present the holding force to the user’s arm. Besides, the winding speed of the belt is changed according to the hardness of the object held by the prosthetic hand. In the control system of the FFB device, a reference input creation model creates reference input signals according to the hardness. A self-tuning proportional-integral-derivative (PID) control method proposed by [7] was employed to adjust the gain of the PID controller based on the state of a target object and control the belt-winding speed of the FFB device following the reference input. For the verification of the effectiveness of the control system for the FFB device, a myoelectric prosthetic hand made by [8] was combined with a control method proposed by [9], and experiments to distinguish among five kinds of springs of different hardness were conducted.
\nSecond, a feedback device of temperature sense (hereinafter referred to as TFB device) was developed by using a Peltier element to present an object temperature when the user touches the object by a prosthetic hand. A temperature prediction algorithm was proposed to shorten the temperature measurement. Besides, the temperature sense differs at each body site. Therefore, the TFB device developed in this study transfers temperature sense felt by the fingertip to the upper arm based on the result of the experiment on temperature sense investigation. Furthermore, experiments to distinguish among five different temperatures were performed to verify the effectiveness of the TFB device. Finally, two-sensory feedback devices were united, and a two-sensory feedback device was built.
\nIn this study, the myoelectric prosthetic hand made by [8] shown in Figure 1(a) is used. The prosthetic hand consists of motors and wires, and the fingers are bent by winding the wires. A pressure sensor is attached to a finger cushion on the prosthetic hand’s index finger, and a temperature sensor is attached at the fingertip of the prosthetic hand’s middle finger.
\n(a) Myoelectric prosthetic hand. (b) positions of electrodes.
The myoelectric prosthetic hand used in this study only has three fingers, namely, the thumb, index finger, and middle finger. Therefore, the prosthetic hand grasps an object by bending the index finger for contact force feedback case and bending the middle finger for temperature sense feedback case. The motion of the index finger and the middle finger is identified by measuring the surface electromyogram (SEMG) of the flexor digitorum superficialis (ch 1) and extensor carpi radialis longus (ch 2) shown in Figure 1(b) to control the proximal interphalangeal (PIP) joint of the prosthetic hand’s index finger and middle finger.
\nIn this study, amputees who lost the lower half of a single forearm were chosen as subjects, and electrodes were placed on the upper half of the forearm to operate a prosthetic hand. To let prosthetic hand users recognize the sense more intuitively, the sense of pressure was given to the prosthetic hand users when they grasp an object. The sense of pressure was presented by the tightening force of a belt on the upper arm of the users.
\nThe difference of the contact force according to the hardness of the object is expressed as the winding speed of the belt. The pressure value added to the finger and displacement of the finger are measured, and they are used to estimate the object hardness. Then, the winding speed of the belt is changed to present the estimated hardness. Namely, the high winding speed is for a hard object, and the low winding speed is for a soft object.
\nFigure 2 shows the developed FFB device and its attached state on the user’s upper arm. The working principle is described as follows. Contact force between an object and a finger is measured by the pressure sensor attached to the finger cushion on the prosthetic hand’s index finger. The main shaft for winding the belt and the motor are connected through two gears. When the prosthetic hand grasps the object, namely, when the contact force is sensed, the motor rotates. Therefore, the main shaft is also rotated by the rotation of the motor. Thus, the belt is winded and tightens the upper arm.
\nFFB device and its attached state.
The device is small with the dimensions 97 mm (width), 117 mm (depth), and 39 mm (height).
\nA safety measure against the motor’s failure or other emergent case needs to be taken. In the case of emergency, the belt is released by simply opening the cover, and then the device is released from the arm.
\nIn this study, a control strategy proposed in [9] is used for the operation method of the myoelectric prosthetic hand. It is well known that an integrated electromyogram (IEMG) reflects muscle activity. Hence, the IEMG is employed to identify the input motion for the operation of the prosthetic hand, and a support vector machine (SVM), which is one of the techniques of the machine learning, is used as an identifier. For the control of the prosthetic hand, a target angle of the finger of the prosthetic hand is set based on how long the user keeps the muscle force. This allows the user to arbitrarily control the finger angle.
\nA pressure sensor “FSR402 Short Tail” made by Interlink Electronics was attached on the fingertip to measure the reaction force 𝐹 [N] from the grasped object. The displacement of the fingertip [m] is measured from the encoder attached on the driving motor of the finger. Then, the spring constant 𝐾 [N/m], hereinafter referred to as the hardness parameter, can be calculated from Hooke’s law:
\nA preliminary experiment was conducted in [10] to derive a conversion formula from the pressure (voltage
With Eq. (2), a reaction force is calculated from the measurement value obtained with the pressure sensor. Thus, one can calculate the hardness parameter from Eq. (1).
\nFor the purpose of this study, the winding speed of the belt in the FFB device needs to be adjustable according to the hardness of the grasped object. A reference input creation model is defined as shown in Figure 3, in which a reference input
Reference input creation model.
The following relation is obtained from Figure 3:
\nA small time constant of the primary delay filter produces a rapidly rising reference input, and a large time constant produces a gradually rising reference input. The time constant
For safety reason, the FFB device is configured so that up to 10 mm of the belt is wound up.
\nA function of the time constant
Numerical simulation was performed to verify the reference input creation model. In the verification, the hardness parameter was increased from 1000 to 6000 for each 1000, and the reference input derived from the reference input creation model was checked. The result is shown in Figure 4.
\nReference inputs.
Figure 4 shows that the rise of the curve becomes rapid as the hardness parameter increases. This result indicates that the reference input could be efficiently created so that the user can feel a difference of the hardness.
\nThe FFB device gives feedback of the force sense by pressing the upper arm of the user. The amount of fat and muscle of the human arm differs from person to person, and the arm hardness could also change depending on how much the user strains the arm. Thus, the arm hardness has a nonlinear characteristic. Therefore, an adaptive control is used for the control of the belt-winding motor of the FFB device. To this end, the self-tuning PID control proposed by [7] is used. Since the self-tuning PID control scheme is based on a discrete time control, Eq. (3) is discretized by a bilinear transformation to design a controller of the FFB device.
\nThe control aim is to determine the control input
Here, 𝑘 is the number of steps. Then, the control input is given by the following equation:
\nFor the verification of the functions of the whole system, the prosthetic hand was operated based on the SEMG of a subject, and the hardness of an object that was grasped by the hand was estimated. Then, how the FFB device controlled by the self-tuning PID could follow the reference input created from the estimated hardness was examined.
\nFive kinds of springs with different hardness were chosen as objects to grasp. Table 1 shows the physical properties of the springs.
\nNo. | \nSpring constant | \nDiameter [m] | \nLength [m] | \n
---|---|---|---|
S1 | \n990 | \n14 × 10−3 | \n25 × 10−3 | \n
S2 | \n1800 | \n8 × 10−3 | \n25 × 10−3 | \n
S3 | \n2980 | \n10 × 10−3 | \n30 × 10−3 | \n
S4 | \n4390 | \n13 × 10−3 | \n25 × 10−3 | \n
S5 | \n5340 | \n7 × 10−3 | \n25 × 10−3 | \n
Physical properties of springs.
The subject was an adult male in 20s. The results in which each of the springs was grasped once are shown in the following figures and tables. Figure 5 shows how the FFB device followed the reference input. Table 2 shows the results of the hardness estimation. Table 3 shows self-tuning PID gains and the time constant calculated from the estimated hardness.
\nReference input and output of the FFB device.
Spring | \nForce [N] | \nDisplacement [m] | \nEstimated hardness parameter [N/m] | \nReal hardness parameter [N/m] | \n
---|---|---|---|---|
S1 | \n5.23 | \n3.76 × 10−3 | \n1390 | \n990 | \n
S2 | \n5.27 | \n2.56 × 10−3 | \n2060 | \n1800 | \n
S3 | \n5.66 | \n1.80 × 10−3 | \n3150 | \n2980 | \n
S4 | \n5.15 | \n1.27 × 10−3 | \n4060 | \n4390 | \n
S5 | \n4.96 | \n0.99 × 10−3 | \n5030 | \n5340 | \n
Estimated and real hardness parameter.
Spring | \nTime constant | \nPID gain | \n||
---|---|---|---|---|
\n\n | \n\n\n | \n\n\n | \n||
S1 | \n1.78 | \n0.22706 | \n0.0125 | \n0.01154 | \n
S2 | \n1.58 | \n0.22707 | \n0.0125 | \n0.01154 | \n
S3 | \n1.06 | \n0.22713 | \n0.0125 | \n0.01150 | \n
S4 | \n0.69 | \n0.22710 | \n0.0125 | \n0.01151 | \n
S5 | \n0.49 | \n0.22717 | \n0.0125 | \n0.01147 | \n
Time constant and self-tuned PID gains.
Figure 5(a) and (b) shows a time delay of about 0.2 s in the response of the FFB device for any spring. However, the device clearly followed the reference input. Although a small error between the estimated value and the real value of the hardness parameter is seen in Table 2, the time constant was successfully calculated for all of the springs as shown in Table 3. Therefore, it was confirmed that the reference input could be created according to the estimated hardness of the grasped object. In addition, the belt-winding action of the FFB device under the control of the self-tuning PID controller followed the reference input obtained from the estimated hardness. Thus, it was verified that the system worked properly.
\nThe usefulness of the FFB device with the proposed system implemented is objectively verified with a psychophysics experiment method. Five kinds of springs, shown in Table 1 in the previous section, were used as the target of the hardness identification.
\nIn the experiment, the myoelectric prosthetic hand was not used, but the spring constant of each spring was input directly to a computer, and then the hardness identification experiment using the FFB device was conducted.
\nThe experiment was conducted by following the procedure of a constant method. The hardness of a brass spring (
FFB device is attached on the upper arm of the subject.
The subject is trained so that he can recognize the behavior of the FFB device.
The standard stimulation is given to the subject.
A 4-second interval is taken.
The comparative stimulation is given to the subject.
The subject answers which stimulation is harder or whether the two are the same.
25 sets of operations [(3)–(6)] are conducted. In the operations, all the comparative stimulations are used five times in random orders.
The operations [(3) and (5)] were replaced, and 25 sets of the operations [(3)–(6)] are conducted again.
The experiments were performed for five healthy subjects in their 20s. In the operations, a 1-min break was taken every five sets to prevent the subject from getting tired.
\nTable 4 shows the results of experiments. The bold numbers show the ratio of correct identification of the stimulations.
\nStimulation | \nRate of the subject’s answer [%] | \n||
---|---|---|---|
Hard | \nEqual | \nSoft | \n|
S1 | \n4 | \n12 | \n|
S2 | \n16 | \n16 | \n|
S3 | \n24 | \n30 | \n|
S4 | \n22 | \n0 | \n|
S5 | \n12 | \n0 | \n
Identification results of hardness.
From the results on the hardness identification experiment, one can see that the proposed method of presenting different varying hardness levels by using different belt-winding speeds was effective to identify the hardness of the five kinds of objects.
\nA combination of cold and warm sensations is called a temperature sense. The temperature sense differs at each body site even when an object of the same temperature is touched. In addition, when the skin is exposed to extreme heat or cold, the pain along with the risk of burns arises. Therefore, it is necessary to regulate the temperature of the TFB device.
\nThe Peltier element is an electronic device that enables both cooling and heating by applying a voltage on the basis of the Peltier effect, and temperature is adjustable by regulating the voltage. The TFB device has a Peltier element; thus, the temperature sense is transferred to the user. The Peltier element used in the TFB device is “TEC1-12708” made by HB Electronic Components.
\nA thermocouple is a temperature sensor on the basis of the Seebeck effect. The thermocouple is attached to the silicone finger mounted on the fingertip of the myoelectric prosthetic hand to measure temperature of an object when the fingertip touches the object. A K-type thermocouple “AD-1214” made by T&D Corporation is used in this study.
\nFigure 6 shows the developed TFB device and its attached state on the user’s upper arm. The Peltier element is attached to the inside of an aluminum board, and in order to raise a heat dissipation efficiency, a radiation sheet and a heat sink are attached to the other side of the aluminum board. The TFB device is attached on the upper arm of the user in contact with the user’s skin, and the temperature sense that is corresponding to the temperature detected by the temperature sensor at the fingertip is transferred in the upper arm of the prosthetic hand user.
\nTFB device and its attached state.
The device is small enough with the dimensions 50 mm (width), 60 mm (depth), and 17 mm (height).
\nWhen the TFB device is used for a long period, the accumulated heat causes a high temperature of the TFB device. Therefore, the continuous operating time of the TFB device is limited to 5 s.
\nWhen the TFB device decreases the temperature, it enables refrigeration of surface temperature to a minimum of 15°C for 5 s. On the contrary, when the TFB device increases the temperature, it enables heating of surface temperature exceeding 50°C. Hence, the temperature of the TFB device is limited to 40°C for safety.
\nAfter the myoelectric prosthetic hand contacts with the object, the temperature sensor needs a long time for measuring the temperature. Therefore, a temperature prediction is performed to shorten the measurement time.
\nLet relationship between a sensor output
To determine the transfer function
Let
where ∆
Let
The predicted temperature is updated to reduce the error when the sensor detected a temperature variation; thus, the temperature when reached to the equilibrium state is given by Eq. (10). As a result, the sensor can detect the temperature of the object in a short time.
\nThe verification experiment was performed to verify an effectiveness of the proposed temperature prediction algorithm. In the experiment, under the room temperature of 26°C, the sensor touched an object of 40°C. Then, the temperature was predicted by the proposed algorithm. Figure 7 shows the result.
\nResult of the temperature prediction for the object of 40°C.
The result showed that prediction of the temperature in a short time is possible by using the proposed temperature prediction method.
\nThe temperature sense of an individual differs at each body site. For example, the temperature senses when an object with the same temperature is touched with a finger and with the upper arm are different. Therefore, in order to investigate the difference in the temperature sense between the fingertip and the upper arm, a temperature sense investigation was performed. Thus, the temperature experienced by the upper arm which is equivalent to the temperature experienced by the fingertip was determined as feedback temperature to the upper arm.
\nThe temperature which should be presented at the upper arm and the voltage which should be applied to the TFB device were determined in [11] as follows. The relationship between the temperatures experienced by the fingertip and by the upper arm was interpolated. Then, the relationship between the predicted temperature at the fingertip
In the previous section, the developed TFB device was controlled in an open-loop system, in which the constant voltage computed from Eq. (12) was applied to the TFB device. In the case where the voltage is continuously provided to the TFB device, the temperature keeps increasing or decreasing. Hence, it is impossible to maintain the temperature using this control system. Therefore, the continuous operating time of the TFB device was limited to 5 s.
\nTo use the TFB device continuously, a closed-loop control system was constructed. For this purpose, another temperature sensor was additionally attached on the surface of the Peltier element of the TFB device. The target temperature in the upper arm
In order to verify the effectiveness of the closed-loop control system with PID controller, experiment was performed. In the experiment, the target temperature is suddenly decreased from 40 to 15°C. The transition of the temperature of the TFB device and the input voltage to the TFB device are shown in Figure 8.
\nTemperature of the TFB device and input voltage to the TFB device.
As shown in Figure 8, the results showed that the constructed closed-loop system enabled the adjustment of the temperature of the TFB device according to the temperature change and also enabled a long-time continuous operation of the TFB device.
\nIn order to verify the performance of the TFB device controlled in the closed-loop control system, a temperature identification experiment was performed. The usefulness of the TFB device controlled by the closed-loop system is objectively verified with a psychophysics experiment method.
\nIn this experiment, the myoelectric prosthetic hand was not used, but each temperature was input directly to a computer, and then the temperature identification experiment using the TFB device was conducted.
\nThe temperature of 30°C was used as standard stimulation, and five kinds of temperature, 28, 29, 30, 31, and 32°C, were used as comparative stimulation. The following describes the experimental procedure:
\nTFB device is attached on the upper arm of the subject.
An experimenter inputs the standard stimulation (30°C) to the computer, and standard stimulation is presented to the subject by the TFB device.
An experimenter inputs the comparative stimulation that is randomly selected from the five kinds of temperatures to the computer, and comparative stimulation is presented to the subject by the TFB device.
The subject answers which temperature is higher or whether the two are almost same.
25 sets of the operations [(2)–(4)] are performed.
The operations [(2) and (3)] were replaced, and 25 sets of the operations [(2)–(4)] are performed.
In the operations, all the comparative stimulations were used 10 times in random orders. The experiments were performed for five healthy subjects in their 20s.
\nTable 5 shows the results of experiments. The bold numbers show the ratio of correct identification of the stimulations.
\nTemperature of comparison stimulus [°C] | \nRate of the subject’s answer [%] | \n||
---|---|---|---|
Hot | \nEqual | \nCold | \n|
28 | \n0 | \n14 | \n|
29 | \n4 | \n36 | \n|
30 | \n6 | \n12 | \n|
31 | \n34 | \n6 | \n|
32 | \n10 | \n4 | \n
Identification results of temperature.
From the results on the temperature identification experiment, one can see that the proposed method of presenting temperature by the TFB device controlled in the closed-loop control system was effective to identify the five kinds of temperatures.
\nTo improve the operability of the myoelectric prosthetic hand, a new myoelectric prosthetic hand was designed and built by imitating the commercial prosthetic hand, which is shown in Figure 9. The pressure sensor and the temperature sensor were attached to the fingertip of the thumb and index finger of the prosthetic hand, respectively. Thus, this myoelectric prosthetic hand makes it possible to detect the force and temperature when the prosthetic hand holds an object.
\nNew myoelectric prosthetic hand.
Finally, the FFB device and the TFB device were united, and a two-sensory feedback device was built, which is shown in Figure 10. The dimensions of the device are 75 mm (width), 82 mm (depth), and 34 mm (height).
\nTwo-sensory feedback device and its attached state.
In this study, force feedback device (FFB device) and temperature feedback device (TFB device) were proposed and built. When a user of a myoelectric prosthetic hand grasps an object, the FFB device provides pressure to the user’s upper arm by winding a belt using a motor, and the TFB device presents the temperature sense to the user’s upper arm using the Peltier element.
\nIn the FFB device, the hardness of the object was estimated by a pressure sensor attached on the fingertip of the myoelectric prosthetic hand, and a reference input was produced by a reference input creation model according to the hardness. In addition, a self-tuning PID controller was employed to control the FFB device so as to make the motor’s output angle follow the reference input. Furthermore, the hardness of the grasped object was presented by the winding speed of the belt. Hardness identification experiment to distinguish among the five kinds of springs of different hardness was carried out. The experimental results on the hardness identification experiment showed that the proposed method was effective to identify the hardness of the five kinds of objects.
\nIn the TFB device, a temperature prediction algorithm was proposed for short-time temperature detection. Then, based on the results of the temperature sense investigation, the corresponding temperature sense when the object was touched by a fingertip was transferred to the user’s upper arm by the TFB device. However, it was difficult to operate the TFB device continuously because this device was controlled in an open-loop control system. To solve this problem, a closed-loop control system was constructed for the TFB device and was tested for sudden change of the temperature. Temperature identification experiment to distinguish among five different temperatures was carried out to verify the effectiveness of the TFB device controlled in the closed-loop control system. The experimental results on the temperature identification experiment showed the sufficient capability of the TFB device controlled in the closed-loop control system.
\nIn addition, a new myoelectric prosthetic hand was built to improve the operability of the myoelectric prosthetic hand. Finally, two-sensory feedback devices were united, and a two-sensory feedback device was built.
\nThe author thanks Mr. T. Morita, Y. Ueda, and M. Isobe for their assistance in experimental works.
\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.
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].
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.
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
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.
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].
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].
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.
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,
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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