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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
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The recent growing demand for energy alternatives to fossil fuels has been a reality shared by many countries in the first few decades of the twenty first century. Economic and environmental issues, population growth, industrial consumption, energy insecurity as well as existing conflicts around the use of raw materials for the production of food types used in the making of fuels, are some of the factors driving governments, universities and multinational corporations to broaden the scalability of their biofuels, such as ethanol, using renewable sources such as lignocellulosic types.
Ethanol can be produced from various raw materials, which can be classified into three categories: (a) simple sugar sources; (b) starch sources; and; (c) lignocellulosic material sources.
As to the technological profile of such categories, when presented in a timeline, they form the technology trajectories representing the production of ethanol, each one related to a specific technological paradigm. Therefore, one considers first generation ethanol ethical alcohol whose production requires raw materials that are rich in saccharosis (sugar cane juice, saccharine sorghum, beetroot, etc.) and/or rich in starch (sweet potato, wheat, potato, corn, cassava, etc.). Regarding second generation ethanol, it is made from biomass that is rich in lignocellulosic materials, such as wood, straw, stems and grass leaves. Finally, third generation ethanol comes from the processing of microalgae biomass after the extraction of lipidic materials (this production modality does not have an industrial representativity yet).
Taking into account this theoretical basis and considering the raw materials that are suitable for ethanol production, as well as the three modalities of the technological trajectory of ethanol production, we conclude that ethanol produced from sugarcane is currently the bioenergy production with the highest yield per unit and higher total energy balance, when we consider the proportion of energy in the final product (ethanol and mechanical energy, thermal and electric) and the fossil energy needed for its production. Besides, sugarcane ethanol offers the possibility of two technology trajectories that are almost consecutive (first- and second-generation productions with the use of sugar cane juice and bagasse).
In this context and in the light of the current technological scenario, this chapter develops an innovative approach to the production of ethanol that comes from sugarcane, combining concepts of patent heuristics with studies of technology trajectories, dependence and paradigms [1]. The study uses technology prospection techniques with analyses of “Breakthrough Inventions,” also applying “Forward citations” for an analysis of future technology affinity. Finally, it seeks to obtain a consolidated profile to forward the technology trajectory of sugarcane-based ethanol production.
The piece is divided into three sections: methodology, results and final conclusions. Results and discussions are, in their turn, subdivided into five subsections: general panorama, breakthrough inventions—geographic and current owner distribution analysis, breakthrough inventions—technology analysis, breakthrough inventions—forward citation analysis and recent innovations and technological advances in ethanol production.
The methodology is based on the study of patent citation and is divided into two stages. In the first stage, patent documents were retrieved with bibliometric analysis carried out through the PatSeer® commercial patent database. It uses keywords such as: alcohol, bioalcohol, ethanol, bioethanol, saccharum, sugarcane, “sugar cane,” bagasse, cellulose, biomass, lignocellulose and molasses. In the title and summary fields, it used the extend family filter. The study made use of Boolean operators “OR,” “AND” and words truncated with asterisk (*). We covered the period between 2000 and 2018, according to the priority date. All the retrieved documents were classified according to the keywords in the title, summary and claim fields, which resulted in the following categories: (i) pretreatment with acid and enzymatic hydrolysis, (ii) fermentation with yeast, bacteria or non-yeast fungus, (iii) distillation and (iv) sugarcane.
The second step was the data analysis per se, composed by:
Evolution over time of patent documents according to priority year, highlighting quoted documents (>5);
Analysis of patent documents (heavily cited > 5) in different types of citations: patent literature—PL (backward and forward), non-patent literature—NPL (references), family size and documents made available. Calculation of self-citations (difference between forward citations (individual and non-self-citation));
Calculation of the patent index citation of “breakthrough inventions” (CPR: citation patent ratio) [2, 3] according to the priority origin country:
A ratio of >1 is good, a ratio of <1 is relatively low.
Analysis of the profile of main authors of “breakthrough inventions”;
Analysis of the interrelation of the technologies in the most cited “breakthrough documents” and the calculation of the technical impact index (TII) of the breakthrough inventions—the percent of patents in a period analyzed, which are in the most highly cited of all the breakthrough inventions. The expected value of the TII has been normalized to equal 1. “A TII below 1 indicates that patents are not especially highly cited” ([3], p. 272).
Analysis of citations of the downstream of breakthrough inventions.
As highlighted in the methodology section, the technology focus of the study is the production of ethanol from sugarcane in its various first-generation (ethanol) and second-generation (bioethanol) modalities. The search strategy used retrieved 223 patent documents in the 2000–2018 period according to the year of priority. Out of those 301 have more than five forward citations by patent family. An expressive range of data on first-generation (ethanol) and second-generation (bioethanol) production were observed positively that when stimulated and directed, there is a growing interest in the patent protection of the intellectual assets (in the form of patent depositories) coming from research and industrial developments (Figure 1).
Distribution over time of patent documents related to the production of sugarcane ethanol, highlighting 301 highly cited documents. Period: 2000–2018. N = 2023. Source: Compiled by the authors, PatSeer® database.
It is worth highlighting again that, on industrial levels, ethanol is considered to be a very relevant biofuel for producer countries, and which can be obtained from various primary and secondary (lignocellulosic biomass types) sources, such as:
through the hydrolysis of starch of cereal grains (corn, sorghum, wheat, triticale, rye, malted barley, rice);
tubers (potatoes);
through direct use of molasses sugar and juice from: (a) sugarcane; (b) saccharin sorghum; (c) saccharin beetroot;
through the breakdown and decomposing of the lignocellulosic structure of biomass materials, followed by processes of saccharification and fermentation, which can happen through intervention with: (I) yeast; (II) bacteria and (III) non-yeast fungus; finally;
by implementation of algae crops, with the potential of a co-production of biodiesel and bioethanol.
The global ethanol production from various raw materials has grown year on year, mainly because of its usability as a fuel (or supplementary fuel), and also thanks to its availability from renewable sources as a result of incentives and social and environmentally friendly credentials. This growth in the global ethanol production noticeable from Figure 2 takes place independently from the struggle between the use of its primary raw materials (grains and sugarcane juices/extracts, sorghum and saccharin beetroot) and food production for the global population.
World ethanol production. Source: KNect365 Energy, 2019.
From an economic point of view, when we compare Figures 1 and 2, we perceive a noticeable alignment of evolutions over time given that the patent system, as it reflects the advances of investments in R&D, reveals the bias that paired the economic development of a nation to its technological development thus highlighting the strong maintenance of interests in the technologies in question. It also important to emphasize that patent data analysis aids significantly to understand technology tendencies as well as forecast future technology perspectives.
This way, with a focus on studies of future technology perspectives, we applied here the analysis of “patent citation” (PC). The methodological effort made here is in line with what many researchers across the globe have been doing for decades, using methodologies based on “patent citation analysis.” This methodology has gained traction and has been developed and adapted to increase access to valuable information among companies, researchers, research centers, universities and countries. The information contained in patent documents reveals the extent and conduction of applied technical research. Therefore, the use of this tool (patents) makes it possible to show that information available in those patent documents overcomes all barriers and can be used for the expansion of the technique and technology development. Therefore, “patent citation analysis” reveals the creation and propagation of information, as well as promotes its applicability in various technical fields which will be able to originate/spawn new technologies [4, 5, 6].
Figure 1 also shows the evolution of highly cited patent documents based on retrieved data (orange bars), whose extraction can be observed in Table 1, which shows a summary of the main quality indicators of the retrieved documents, comparing the total number of retrieved documents in comparison with the most cited ones.
Document quality indicators retrieved | Total | Most highly cited (>5) (Percentage of total) |
---|---|---|
No documents | 2023 | 301 (14.9%) |
No. of extended family members | 5128 | 811 (15.8%) |
NPL—non patent literature: | ||
No. of references | 1612 | 642 (39.8%) |
PL—patent literature: | ||
No. of backward citation | 5585 | 1780 (31.9%) |
No. of forward citations (individual) | 6807 | 5280 (77.7%) |
No. of non self citations (forward citation) | 5054 | 3954 (78.2%) |
Auto-citation | 1753 | 1326 (21.8%) |
Granted | 685 | 137 (20%) |
Average year | 2011.4 | 2008.1 |
Main quality indicators of retrieved documents.
Source: Compiled by the authors, PatSeer® database.
We can see that around 78% of the individual forward citations concentrate in 15% of retrieved documents, denoting a high concentration around specific technology nuclei, while 25.1% of individual forward citations also refer to self-citations of patent documents.
Another very relevant information from Table 1 refers to the relation between the values of “patent literature” (PL) and “non-patent literature” (NPL). According to Demet et al. [7], this relation (PL/NPL) infers a state of industrial maturity hoped to be reached. In other words, values below the first inferior quarter (>25%) suggest a favorable state for innovation and the commercialization of products/processes of a given technology sector. Therefore, it is possible to conclude there are well-established maturity nuclei in detriment of the possibility of the existence of nuclei that are not mature yet. A better definition of these maturity nuclei was set out by “breakthrough inventions” study of “patent citations” [8].
According to Yan et al. [9], “breakthrough inventions” can be understood as inventions that aspire to or serve as technology bases for the creation of subsequent inventions. They are inventions that are a relevant source of competitive edge and can be part of a viable strategy to boost a company” capacity to generate innovative inventions. They can help meeting the challenge to create radical/disruptive inventions through the recombination of non-redundant knowledge, mainly by using patent publications of industrial competitors’ patent publications. In this case, the technology sector of first- and second-generation ethanol production.
Kerr [10] used “breakthrough inventions” to identify important areas for future research in the area. Similarly, Egli et al. [11] used “breakthrough inventions” to identify and induce applied technologies to climate change mitigation. This way, in this paper we used such studies as reference in the investigation of the efforts and technology maturity, patenting growth and the influence of patents in the technology development of first- and second-generation ethanol production. This way, this work presents “breakthrough inventions” through “patent citations” with an analysis of the main technology clusters within the ethanol production sector and its temporal and spatial migrations.
Before we continue with the present analysis, it important to understand the relevance of the study on geographic distribution and the owners of technologies in “breakthrough inventions.” Therefore, the analysis of components of geographical distribution and the ownership of inventions is key as it provides information on the flow of knowledge of the analyzed technology [4]. For that matter, we drew from Kaki’s study on citations performances ratio (CPR). CPR comes from a comparative study based on the presence of highly cited patents in a given patent database, a specific timeline and category. The values whose ratio are bigger than the unit (CPR > 1) indicate a good performance. According to Narin and Olivastro” study [12], any patent document cited 06 (six) or more times can be considered as very relevant for the “patent citation analysis.” They can also be considered “breakthrough inventions.”
In this sense, Table 2 sums up the main indicators of patent quality according to the country of origin of the priority request. The importance of analyzing this parameter is to understand which countries dominate the technology. Only the USA, China and Japan have CPR numbers above 1, which are considered good. Other countries did not obtain a good performance during analysis.
Priority country | No. of records | CPR | % granted of the priority country | % of extended family members |
---|---|---|---|---|
United States | 61 | 8.35 | 42.6 | 61.7 |
China | 172 | 6.21 | 50.6 | 23.7 |
Japan | 52 | 2.53 | 32.7 | 8.6 |
Germany | 5 | 0.18 | 0.0 | 2.2 |
Korea | 4 | 0.11 | 50.0 | 1.5 |
Czech Republic | 2 | 0.06 | 50.0 | 0.9 |
Russian Federation | 2 | 0.04 | 0.0 | 0.6 |
Brazil | 1 | 0.02 | 100 | 0.5 |
France | 1 | 0.02 | 100 | 0.2 |
United Kingdom | 1 | 0.02 | 100 | 0.1 |
Total | 301 | 45.2% | 100% |
Country of origin profile analysis of “breakthrough inventions.”
Source: compiled by the authors, PatSeer database.
When we analyze Table 2, we can see a strong performance by the United States as the conductor of technology within the analyzed setting. Therefore, even if it does not have its ethanol matrix focused on sugarcane crops, the United States present a relevant patent achievement in terms of “breakthrough inventions”. This suggests technology leadership in related areas when a sugarcane matrix is used. Also relevant is the fact that the United States are the biggest ethanol producers in the world, followed by Brazil, EU, China and Canada (Figure 3) while the largest sugarcane producer are Brazil, India, China, Thailand and Pakistan [13].
Global ethanol production by country of 2018 (country; million gallons; share of global production). Source: RFA analysis of public and private data source.
Following the same logic, we can see that China plays an important role in the “breakthrough inventions” analyzed scenario, that is, it appears as one of the five global ethanol powers, as well as one of the five countries with the highest number of innovative inventions. We should highlight here that the Chinese government is planning the implementation of a policy of an E10 ethanol addition to gasoline across its territory by 2020. This will be very important for countries like the United States and Brazil, whose CPR of the latter is only 0.02. Such piece of information about Brazil (CPR = 0.02) may suggest a strong dependence and even propensity to the technology “colonization” in specific sub-sectors and the existence of “Patent Pools” [14, 15] and “Patent Trolls” [16, 17].
Regarding the profile of the main holders of “breakthrough inventions” retrieved during the CPR analysis, Table 3 shows the importance of Chinese companies. This is a very important piece of information for this analysis of technology trajectory because it enables a clear visualization of the steps taken by companies and Chinese university research centers toward control and technology independence of methods of first- and second-generation ethanol production.
Current owner | No. records | CPR | No. granted | Sugarcane | Biomass | Pretreatment | Fermentation | |||
---|---|---|---|---|---|---|---|---|---|---|
Acid hydrolysis | Enzymatic hydrolysis | Yeast | Bacterium | Fungus without yeast | Distillation | |||||
China petroleum & chem-sinopec | 9 | 0.27 | 9 | 1 | 3 | 3 | 4 | 5 | 0 | 4 |
Univ tsinghua | 8 | 0.32 | 8 | 4 | 3 | 3 | 4 | 3 | 1 | 4 |
Tsukishima kikai Co Ltd | 7 | 0.32 | 2 | 0 | 2 | 2 | 1 | 0 | 0 | 0 |
Univ tianjin | 7 | 0.29 | 5 | 2 | 0 | 1 | 4 | 1 | 1 | 5 |
Toshiba corp | 5 | 0.12 | 0 | 0 | 0 | 1 | 2 | 0 | 0 | 0 |
Oji holding corp | 5 | 0.20 | 4 | 0 | 0 | 0 | 1 | 0 | 0 | 2 |
Inst process Eng Cas | 4 | 0.13 | 0 | 0 | 0 | 1 | 2 | 0 | 0 | 3 |
Hitachi group | 3 | 0.10 | 1 | 0 | 0 | 0 | 0 | 0 | 0 | 1 |
Cofco Ltd | 3 | 0.10 | 3 | 0 | 2 | 3 | 3 | 3 | 0 | 0 |
Dalian chem physics inst | 3 | 0.08 | 3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Analysis of the profile of the main patent holders of “breakthrough inventions”.
N = 301. Source: Compiled by the authors, PatSeer® database.
Although the companies listed in Table 3 show low CPR (<0.5), an indicator they produce little impact with the dissemination of their technologies, their respective values often surpass by several times the CPR of countries like Germany (2.8×); Russia (12.5×); Brazil (25×); and France (25×).
Also relevant is the fact that the number of “breakthrough inventions” documents retrieved from these companies and Chinese universities present low statistical dispersion (average standard deviation = 1.88). This, however, suggests something positive. These figures can indicate a cohesive movement of technology ascension for the sector, cluster or grouping formation. We must also call attention to the high number of documents made available by these actors, except for Toshiba Corp, Institute of Process Engineering, and the Chinese Academy of Sciences, who until the time when the analysis was made did not have patents issued for the technologies herein studied.
The analysis of Table 3 also reveals the absence of actors from other countries. For example, the presence of actors such as the United States and Japan merely indicates them to be countries with a considerable number of “breakthrough inventions” documents. However, it can be concluded there is great dispersion of patent document ownership, which in its turn suggests an open and competitive market, without business clusters. Regarding the technology aspect of ethanol production, Table 3 reveals to readers that the great intellectual effort by Chinese companies is in areas such as: (i) pretreatment of raw materials (hydrolysis); (ii) fermentation; and, (iii) post-treatment (distillation); in that order.
From that point of view, Figure 4, created from 301 “breakthrough inventions” documents-corroborates previous understandings of Table 3 analysis, showing a relationship between actors and technology areas in each category. Therefore, it is possible to verify a certain level of non-binding cohesion among the analyzed actors, there being no sharing of technology in those supposed partnerships.
Relationship network among the 10 main holders of technologies associated to the production of ethanol, “breakthrough inventions” and biomass categories (sugarcane), pretreatment (acid hydrolysis and enzymatic hydrolysis), fermentation (yeast, bacterium and yeast-free fungus) and distillation. N = 301. Source: Elaborated by the authors, PatSeer® database.
China Petrochem Corp (Sinopec) appears as an exception to the block composed by all the other actors. The data suggests low adhesion by that company to the cluster formed by other companies and universities. There seems to be no apparent link between them and no effort of interaction among them.
In the case of technology associated to the production of ethanol, the “breakthrough inventions” and the analysis of biomass (sugarcane) analysis, pretreatment (acid hydrolysis and enzymatic hydrolysis), fermentation (yeast, bacterium and yeast-free fungus), post-treatment (distillation) indicates possible dispersion.
In 2016, the United Nations Conference on Trade and Development (UNCTAD) [18] launched a report where they laid out the main distinctions between first and second generation renewable fuels, based on their raw materials’ features (Table 4). Therefore, Table 4 shows that first generation biofuels are made from seeds, cereals and sugar types (from extracts and juices) while second generation biofuels are produced from the pretreatment of cellulosic and lignocellulosic biomass, such as: carbonaceous materials of renewable vegetable sources (wood, bagasse, straw, barks, grass, etc.).
First-generation biofuels (from seeds, grain and sugar) | Second-generation biofuels (from lignocellulosic biomass, such as crop residues, woody crops or energy grasses) |
---|---|
Petroleum-gasoline substitutes
| Biochemically produced Petroleum-gasoline substitutes
|
Petroleum-diesel substitutes
| Thermochemically produced Petroleum-gasoline substitutes
|
Thermochemically produced Petroleum-diesel substitutes
|
Differences between the production of first- and second-generation biofuel according to raw materials.
Source: UNCTAD [18].
In order to comply with the time-based interval adopted in this paper, it is necessary to highlight that the conversion of lignocellulosic biomass materials into biofuel was already viable in the mid-2000s and, on an industrial level, biofuels derived from this process involving enzymatic stages were not a common practice nor were they produced in great volumes for the market before the year 2005 [19]. Besides, it is possible to notice a significant change in the alcohol (ethanol) production from 2005 onwards (see Figure 2), the year when the Kyoto protocol was signed by most ethanol-producing countries and regions. At first, China and the United States did not agree to sign the protocol. However, after discussions that lasted more than half a decade, those countries ratified the protocol and started a global pact aimed at mitigating the production of greenhouse gases, in 2011 [20].
This global agreement directed, once and for all global efforts and interests in ethanol-producing technologies from lignocellulosic materials (biomass route: Figure 5). This way, it boosted their sustainability footprint and benefits for the environment and also appeased disputing parts regarding sources of raw materials to be used to produce energy in detriment of food for people, as is the case of sugarcane in Brazil and China [21].
Schematic representation of the stages of second-generation ethanol production. Source: Elaborated by authors.
In this sense, after 2013 the whole political debate about the implementation of second-generation fuels became a new reality of technological-industrial trajectory, while for example, ethanol coming from lignocellulosic materials (vegetable biomass and cellulosic residue) began to be produced at industrial/commercial scale (Table 5), representing an opportunity for a number of countries to be inserted technologically and take part of the emerging industry of second generation biofuels [18].
Biofuel type and production capacity (millions of liters per year) | ||||||||
---|---|---|---|---|---|---|---|---|
Fuel | 2009 | 2010 | 2011 | 2012 | 2013 | 2014 | 2015 | 2016 |
Advanced Ethanol | 27.71 | 42.36 | 46.52 | 922.62 | 2.522.22 | 4.770.26 | 8.538.41 | 8.848.82 |
Cellulosic Sugars Ethanol | 0.00 | 0.04 | 0.08 | 0.08 | 3.82 | 3.82 | 102.21 | 102.21 |
Biofuel type and production capacity.
Source: Biofuels digest, 2011. Note: 2012–2016 data represents 2011 estimates.
As we can see from Table 5, the advanced route of ethanol production, similarly to biomass route (cellulose), gains momentum from 2013, when several new technologies started to be implemented in the industrial field. This way, using studies on clusters of the topic-based documents of “breakthrough inventions” as a departing point, a series of more detailed analysis was carried out about the technology profile of the main routes of ethanol production (Figure 6).
Graphic representation of the topics in documents of patents of “breakthrough inventions”. Source: Compiled by the authors, PatSeer® database.
By reading Figure 6, we can see that technology linked to the Ethanol Fermentation phase and pre-treatment (Alcohol Production) are the base of new technology trajectories in the production of ethanol. The image allows us to see subsections related to the conversion of cellulose into ethanol, as well as the treatments with the use of acids and enzymes for the preparation of sugars that will be consumed by microorganisms during fermentation. Regarding the raw materials the analysis in Figure 6 comprises, it is possible to see the technological inclination toward the use of biomass material (lignocellulosic) as a pillar for the technology trajectory in the production of fuel alcohol that will continue into coming years. The greater emphasis is on the biomass material that is not consumable by humans and animals, especially the waste from the lignocellulosic base.
As a way to corroborate this timely analysis, Table 6 shows the relation of the 10 main international classifications of patents with the biomass categories (sugarcane), pre-treatment (acid and enzymatic hydrolysis), fermentation (yeast, bacterium, yeast-free fungus) and post-treatment (distillation). We noticed the main classification is C12P (fermentation or enzyme-using processes to synthesize a desired chemical compound or composition or to separate optical isomers from a racemic mixture), with a TII higher than one (3.67), proving to be a relevant technology field for the production of ethanol. The most representative categories were related to yeast and distillation, because during the ethanol production process, both first and second generation, fermentation and distillation are crucial. However, TII for both was low (0.37).
IPC | No. records | TII | Biomass | Pretreatment | Fermentation | Posttreatment | |||
---|---|---|---|---|---|---|---|---|---|
Sugarcane | Acid hydrolysis | Enzymatic hydrolysis | Yeast | Bacterium | Fungus (without yeast) | Distillation | |||
C12P | 1105 | 3.67 | 130 | 322 | 363 | 562 | 264 | 35 | 379 |
C12R | 370 | 1.23 | 50 | 139 | 151 | 261 | 135 | 15 | 125 |
C12N | 260 | 0.86 | 23 | 47 | 56 | 151 | 80 | 17 | 54 |
C07C | 200 | 0.66 | 17 | 20 | 14 | 18 | 4 | 1 | 71 |
C02F | 126 | 0.42 | 7 | 2 | 2 | 11 | 16 | 4 | 25 |
C12M | 110 | 0.37 | 13 | 16 | 19 | 35 | 16 | 3 | 47 |
C10L | 107 | 0.36 | 10 | 17 | 19 | 20 | 16 | 2 | 42 |
C08L | 99 | 0.33 | 1 | 8 | 1 | 2 | 12 | 0 | 18 |
B01J | 78 | 0.26 | 0 | 7 | 2 | 0 | 0 | 0 | 8 |
B01D | 63 | 0.21 | 6 | 4 | 5 | 3 | 1 | 0 | 32 |
TII | 0.11 | 0.23 | 0.25 | 0.37 | 0.18 | 0.03 | 0.37 |
List of the top 10 IPC main class with document classification according to “breakthrough inventions” patent technology process, and technical impact index–TII.
N = 301. C12P: Fermentation or enzyme-using processes to synthesize a desired chemical compound or composition or to separate optical isomers from a racemic mixture; C12R: Indexing scheme associated with subclasses; C12N: Micro-organisms or enzymes; compositions thereof; C07C: Acyclic or carbocyclic compounds; C02F: Treatment of water, waste water, sewage or sludge; C12M: Apparatus for enzymology or microbiology; C10L: Fuels not otherwise provided for; natural gas; synthetic natural gas obtained by processes; C08L: Compositions of macromolecular compounds; B01J: Chemical or physical processes; B01D: Separation. Source: Compiled by the authors, PatSeer® database.
Based on the data in Table 6, it must be highlighted that the classification code C12P, (Fermentation or enzyme-using processes to synthesize a desired chemical compound or composition or to separate optical isomers from a racemic mixture) was the main classification for the analysis, using a TII above one (3.67), a technology field that is essential for ethanol production. Meanwhile, the other technology categories (IPCs) involved in the ethanol process have proven to be statistically with TII impacts but without major discrepancies or significant dispersion (average TII = 0.434; Average deviation = 0.163). They are hierarchically ranked in the relevance sequence that follows: (1st): Fermentation technologies (Yeast, Bacterium and Yeast-free Fungus), because both in first and second generation, fermentation is a crucial stage to obtain ethanol. (2nd) pre-treatment technologies (Acid and enzymatic hydrolysis- slight tendency toward the latter); finally (3rd) Post-treatment technologies (Distillation). This hierarchical configuration can be confirmed in Figure 7, which shows the relation between all networks of relationship between technology clusters.
Networking of the top 10 IPC Main class and the categories (pre-treatment = acid hydrolysis, enzymatic hydrolysis; fermentation = yeast, bacterium, fungus without yeast; distillation), (A) and density graph of the same networking (B). Source: Compiled by the authors, PatSeer® database and VOS viewer visualization [22].
Still looking at Figure 7A and B it is possible to see strong and direct relations between the stages of the ethanol production process, especially between the pre-treatment and fermentation stages, which are interrelated and form a network of weak knots. But when isolated, they are intense. We can observe that, together, such stages make up the central technology focus of ethanol production.
In the sequence, we present some of the most highly cited patent documents of “breakthrough inventions” within the context of previous analysis.
WO2003078644-A2 (25 September 2003): Conversion of cellulose to glucose involves treating a pre-treated lignocellulosic substrate with cellulase.
WO2006007691-A1 (26 January 2006): Obtaining a product sugar stream from cellulosic biomass, involves hydrolyzing a neutralized cellulosic biomass with cellulase enzymes.
WO2006110900-A2 (19 October 2006): Production (P1) of ethanol comprising biomass with aqueous solution containing ammonia, a saccharification enzyme consortium to produce fermentable sugars, and a fermentation conditions with a suitable biocatalyst to produce ethanol.
JP4522797-B2 (11 August 2010): Pre-processing of lignocellulose-containing raw material for use in ethanol production.
JP5233452-B2 (10 July 2013): System for saccharification and fermentation of woody biomass raw material, by adding cellulose degrading enzyme, hemicellulolytic enzyme and alcohol fermentation microorganism.
BR200100762-A (06 November 2001): The method involves grinding lignocellulosic biomass (LB) followed by steam-explosion pre-treatment.
Currently, the analysis of “Forward Citation” is often used by authors of non-patent literature when the objective is a better understanding of patterns, for example, of formation of a portfolio of patent documents for a systematic analysis of the international codes of patent classification. Carpenter, Narin and Woolf [23] and Trajtenberg [8], in their respective works, managed to measure the relationship between “Forward Citation” and the future value of an invention, therefore the “Forward Citation” number that a given patent document receives, and which accumulates over time, is related to the significant technology impact of the technical content of those documents (that is, “breakthrough inventions”). That suggests that patents with a high number of citations have a relevant technology impact and contribute significantly to the advance of technology [24].
Keeping that in mind, it was necessary for the present analysis of investigation of the technology trajectory for the field of first and second generation ethanol production sector to use “Forward Citation” analysis as a “proxy” for the measurement of intangible added value that those “breakthrough inventions” documents really have. This way, under the prism adopted by this study, it was noted that: the more valuable a patented technology, the newer the incentives are created from past learnings; this way, looking at it from an economic point o view, “Forward Citation” results in the measurement of the valuing of those documents of “breakthrough inventions”.
This way, the “Forward Citation” analysis of the 301 documents of “breakthrough inventions” was carried out by taking into account the codes of international classification of patents retrieved in previous analyses (Figure 8). From that analysis it was possible to identify: (i) 3506 patent documents in “forward citation”; and, (ii) 1524 patent documents in “backward citation”; the main classifications in the documents in (i) were: (a) C12P7 (count-1337); (b) C12P19 (count-532); (c) C07C29 (count-434); and, (d) C12M1 (count-359).
Analysis of citations of breakthrough inventions. Source: Compiled by the authors, PatSeer® data.
Still looking at Figure 8, it is possible to note that the ratio between the quantity of retrieved documents to (i) “forward citation” and (ii) “backward citation” outnumbers the unit by 2.3 times, thus indicating that the 301 “breakthrough inventions” documents analyzed in this study presented a strong impact on subsequent technology generations [25].
Moving on, the 3506 patent documents in “forward citation” were treated and filtered through extended family, resulting in 2406 original documents of patent family (no document doubling). These were equally stratified and analyzed according to technology categories and international codes of patent classification (IPC), which resulted in Table 7.
IPC full class | No. records | Biomass | Pretreatment | Fermentation | Post-treatment | |||
---|---|---|---|---|---|---|---|---|
Sugarcane | Acid hydrolysis | Enzymatic hydrolysis | Yeast | Bacterium | Fungus (without yeast) | Distillation | ||
C12P7/10: Substrate containing cellulosic material | 460 | 56 | 165 | 192 | 179 | 59 | 0 | 95 |
C12P7/06: Ethanol | 362 | 50 | 61 | 75 | 147 | 57 | 0 | 75 |
C12P19/14: Produced by the action of a carbohydrase | 262 | 38 | 95 | 133 | 64 | 29 | 0 | 41 |
C12M1/00: Apparatus for enzymology or microbiology | 167 | 24 | 29 | 33 | 32 | 12 | 0 | 45 |
C12P19/02: Monosaccharides | 161 | 21 | 61 | 72 | 22 | 11 | 0 | 10 |
C12R1/865: Saccharomyces cerevisiae | 149 | 22 | 47 | 63 | 112 | 47 | 0 | 31 |
C13K1/02: By saccharification of cellulosic materials | 148 | 18 | 50 | 33 | 10 | 6 | 0 | 10 |
C12P7/16: Butanol | 114 | 23 | 39 | 32 | 25 | 17 | 0 | 27 |
B09B3/00: Destroying solid waste or transforming solid waste into something useful or harmless | 113 | 8 | 14 | 19 | 16 | 6 | 0 | 23 |
C12P7/08: Produced as by-product or from waste or cellulosic material substrate | 113 | 11 | 26 | 29 | 42 | 12 | 0 | 39 |
List of top 10 IPC full class with document classification according to the technology process of forward citation of “breakthrough inventions” patents.
N = 2406. Source: Compiled by the authors, PatSeer® database.
Analyzing Table 7 in relation to Figure 7A and B, it is possible to see there is a prevalence of subclass C12P in detriments to other classification codes (IPC). This highlights that the technology trajectory in analysis is clearly directed to the production of second generation ethanol, through the use of cellulosic waste (biomass).
This information can be inferred by the sequenced information of the main classifications, as follows: (i) C12P7/10: Substrate containing cellulosic material; (ii) C12P7/06: Ethanol; (iii) C12P19/14: Produced by the action of a carbohydrase (set of enzymes that catalyzes 5 types of breakdown during carbohydrates into simple sugars); (iv) C12M1/00: Apparatus for enzymology or microbiology; (v) C12P19/02: Monosaccharides; (vi) C12R1/865: Saccharomyces cerevisiae; (vii) C13K1/02: By saccharification of cellulosic materials; (viii) C12P7/08: Produced as by-product or from waste or cellulosic material substrate. Besides, there is emphasis on the use of enzymes during the initial stage of pre-treatment of raw materials through enzymatic hydrolysis.
This way, it is clear that the stages of pre-treatment and fermentation are the strongest and most relevant technology nuclei for the sector in the near future.
The theory of trajectory and technology paradigm that we use these days were laid out and drafted by Dosi [1]. In his study, the researcher adopted similarities in the process of innovation to incremental innovation and disruptive innovation, to the assessment of process of diffusion between science and technology, taking into account heuristics methodology, well-structured in the form of a strategy of search that directed toward the solution of problems under the existing paradigms. The heuristics sustained by the author, in thesis, boosts incremental innovation in the context of a given technology trajectory, like a driving force that unleashes changes for new trajectories or technology paradigms through the disruptive or radical innovation [1, 26]. Therefore, the heuristics seems to be essential for a better comprehension of the dynamics of the technology involved in ethanol production.
In this analytical context, a new heuristic context was created for the final part of this study, which enable the making of data profiling, on various levels: (i) geographical; (ii) temporal; and, (iii) technological; employing the same data on the family documents of the “forward citation” in a scenario of recent deposits—between 2017 and 2018. This led to Figure 9 and Table 8 as shown in sequence.
Country of origin of “forward citations” for 2017 and 2018. Source: Compiled by the authors, PatSeer®.
IPC main | Sugarcane | Pretreatment | Fermentation | Post-treatment |
---|---|---|---|---|
C08L | 2 | |||
C10L | 1 | |||
C12N | 1 | 4 | ||
C12P | 1 | 2 | 3 | |
C11C | 1 | |||
D21B | 1 | 1 | ||
D21C | 1 | 1 | ||
Total Geral | 2 | 7 | 9 | 1 |
Main IPC related to categories.
Source: Compiled by the authors, PatSeer®.
By analyzing the data set in Figure 8 and Table 8, it is possible to infer that the technology trajectory from the data mined points to China as the country with the biggest technology power to rise in the future and replace the United States as the leader of ethanol-producing technologies, mainly in technologies related to the enzymatic pre-treatment and the fermentation stage. It is worth highlighting the presence of patent documents on the technologies that use modified bacteria and/or yeast-free fungus, which process the raw cellulosic material, and alternately absorb the stages of pre-treatment and fermentation of sugars resulting from the saccharification of lignocellulosic matter in one stage only (see: CN105154416-B, 2018; CN108603186-A, 2018; CN106755011-A, 2017; IN201741014528-A, 2018; IN201831041905-A, 2018; US2018230420-A1, 2018; BR102016030305-A2, 2018).
The study highlights some considerations to be taken up in a broader research agenda in sugarcane ethanol’s production chain.
The first point is that the strategy of patent data retrieval used by the authors in this and other works and for a smaller spatial dimension proved totally valid to characterize technological advances in the aforementioned production chain at the global level. This reveals that the methodology experimented by the authors involving the use of the technological information contained in the patent documents consorted to the specific study of patent citations are very adequate to identify and understand the technology trajectories resulting from investment decisions, research and public policies related to the study of industrial sectors.
A second point to be considered concerns the dynamism of research on second generation technologies for ethanol production from sugarcane in the early years of the twenty-first century. However, what stands out is the prominence of the Chinese research system and its articulation with companies in areas of extremely high complexity, such as biotechnology, especially in the areas of fermentation and enzymatic processes.
Finally, looking at the Brazilian ethanol research and production system, the study indicates routes to be followed and bridges to be built in case the country should want to retake the leading role it has played in this sector in the twentieth century. And this is an important feature of the methodology used in this study that, in prospecting and extracting data and information from the patent system, stripped relevant sources of technological knowledge and research and development networks with which it will be essential to establish partnerships for the development of a collaborative work.
There 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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