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Acknowledgment

I would like to thank Dr. S. Vijayalkshmi for providing this rare and wonderful opportunity to work in the premises of a world renowned institution such as Indian Institute of Technology, Bombay. Im even more grateful to her for providing me a piece of work that has great academic and industrial value. I would like to thank Mr. Sridhar Dalai, who was my mentor, well-wisher and an adviser throughout my project and helped me successfully nish it. Apart from the main work, he taught me numerous subtle but crucial tips that helped expand my practical knowledge about research and many other vital things. I would like to thank Ms. Pragya Shrivastava who was also very supportive during the work and helped me learn some concepts that were fundamental to my work. I would like to thank Mr. Arun Kumar and other labmates who helped me learn the practical know-hows of academic research work. I would like to thank Dr. R P Singh and all the faculty of Amity Institute of Nanotechnology for providing me with the prerequisites for this project. Lastly, I would like to thank my parents without whom nothing of this would have ever happened.

Abstract
Hollow glass microspheres are ne free-owing particles[1] that are sized between 1 to 140m. They have an intrinsic pore structure that are size in the nanometer range which is the result of a specially developed fabrication process called spheroidization. In this process pulverized amber glass particles are passed through a ame at very high temperature during which the feed particles melt to form spheres with central cavity and pores eventually retaining the shape after cooling. HGMs are produced this way for the purpose of hydrogen adsorption and storage, however the amount of adsorption which is immensely dependent on the enthalpy of system is limited by the insulating properties of glass. This limitation is overcome by coating the surface of HGMs by metal oxide. Adsorption studies were conducted on these metal coated HGMs using Sieverts apparatus. It was found that HGMs with metal loading at 2 wt.% lled the highest amount of hydrogen inside the cavity of microspheres. This was attributed to optimum pore density, pore width and metal deposition obtained at this concentration.

Contents
1 Introduction 2 Literature review 3 Experimental 3.1 Preparation of glass frits: . . . . . . . . . . . . . . . . . . . . . . . . . 3.2 Preparation of metal loaded HGMs: . . . . . . . . . . . . . . . . . . . 3.3 Characterization: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 Results and discussion 4.1 Cobalt loaded samples: . . . 4.1.1 FTIR studies: . . . . 4.1.2 XRD studies: . . . . 4.1.3 E-SEM: . . . . . . . 4.1.4 FEG-SEM: . . . . . 4.2 Zinc loaded samples: . . . . 4.2.1 FTIR studies: . . . . 4.2.2 XRD studies: . . . . 4.2.3 ESEM: . . . . . . . . 4.2.4 FEGSEM: . . . . . . 4.3 Magnesium loaded samples: 4.3.1 FTIR studies: . . . . 4.4 Adsorption studies: . . . . . 5 Conclusion 6 8 12 12 12 15 16 16 16 17 18 19 20 20 21 22 22 23 23 24 27

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List of Figures
2.1 3.1 3.2 3.3 3.4 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 4.10 4.11 4.12 4.13 Schematic diagram of Sieverts appratus. . . . . . . . . . . . . . . . . Schematic representation of spheroidization. . . . . . . . . . . . . . . (a) Experimental setup for spheroidization. (b) Heating setup. . . . . [From left to right] (a)FTIR system (b) XRD system (c) ESEM system FEGSEM system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . FTIR spectra images for low and high concentration Cobalt loaded samples. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . XRD graphs for low and high concentration Cobalt loaded samples. . ESEM images of cobalt loaded samples with (a) 0.5, (b) 2, (c) 5 and (d) 10 wt.% concentration. . . . . . . . . . . . . . . . . . . . . . . . . FEG-SEM images of a) 3, b) 5 and c) 10 wt.% concentration. d) EDX image of 10 wt.% concentration. . . . . . . . . . . . . . . . . . . . . . FTIR spectra images for low and high concentration Zinc loaded samples. XRD graphs for low and high concentration Zinc loaded samples. . . E-SEM images of zinc loaded samples with (a) 0.5, (b) 2, (c) 5 and (d) 10 wt.% concentration. . . . . . . . . . . . . . . . . . . . . . . . . . . FEG-SEM images of (a) 5 wt.% and (b) 10 wt.% concentration, (c) magnied patches of 5 wt.% and (d) 10 wt.% concentration. . . . . . FTIR spectra images for low and high concentration Magnesium loaded samples. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Adsorption graphs for cobalt samples. . . . . . . . . . . . . . . . . . . Graphs showing the trend of adsorption values in cobalt loaded samples Adsorption graphs for zinc samples. . . . . . . . . . . . . . . . . . . . Adsorption graphs for magnesium samples. . . . . . . . . . . . . . . . 10 13 14 15 15 16 18 19 19 20 21 22 22 23 24 25 25 26

List of Tables
3.1 List of metal loaded HGMs samples at dierent concentrations . . . . 14

Chapter 1 Introduction
Advancement in technology and fast spreading development across the globe has increased energy consumption drastically and has also caused a severe rise in carbon foot-print. Accounting to this since the last decade focus has been on Green energy which advocates the use of renewable and clean resources for harvesting daily energy requirements. The most commonly discussed resources of Green energy have been bio-fuel, geothermal, solar power, hydrogen fuel, etc. Considering some major factors like wide range of applications, output eciency, cost, reliability and high energy density by mass[2] hydrogen fuel has been one of the most favored contender. It has also made a successful entry into many commercial applications such as fuel for locomotives, laptop batteries, power sources for computers on-board the ISS, etc. Storage of hydrogen has always been a challenge because of its high ammability. Many storage methods including liquefaction, high-pressure gas storage and adsorption onto solid surfaces have been practiced. However the highest potential for storage has been shown by solid-state materials because of their safety and volumetric eciency.[2] There are many types of solid materials such as metal hydrides, carbon nanospheres, microspheres, etc. among which hollow glass microspheres (HGMs) is found to have the highest volumetric eciency, gravimetric eciency and cost eectiveness.[3] These facts support the point that HGMs are one of the most viable solid-state storage medium of hydrogen eventually green energy. Though HGMs is suitable for green energy in general, it also depends on the composition of the starting material from which they are made. There are majorly two dierent compositions that are considered for conversion into HGMs, namely, borosilicate glass and amber glass, out of which the latter have been preferred over the former. This advantage arises from the fact that amber glass does not contain boron as compared to borosilicate glass thus making it a homogeneous material by avoiding the formation of two dierent phases: borate and silicate. Moreover, sulphur dioxide gas, water vapor and other gases, depending on pre-processing, are liberated during the production of amber HGMs resulting in the formation of an intricate porous network within the walls of the HGMs adding to their advantage.

Attributing to these facts, our work focuses on using amber HGMs for hydrogen storage. However, there are some physical limitations of this technology that have to be overcome. HGMs, albeit being one of the most ecient material for hydrogen storage, limits the maximum amount of weight percentage achievable during adsorption due to its thermal insulating properties. This is because gas adsorption is directly aected by the thermodynamics of any system. However, adsorption alone does not result in the storage of hydrogen, diusion also plays a major role in channelizing the transport of gas molecules through the intricate porous network present in the walls of the microspheres. Moreover, since diusion of gas molecules occurs purely by the act of Brownian motion there is a major dependence on thermodynamics. That said, in order to improve the thermal conductivity and subsequently thermodynamic eciency of HGMs a viable method has to be adopted. In light of governing factors such as energy eciency, cost and complexity, coating the surface of HGMs in-situ with conducting material stands to be the best method for improving the adsorption properties of HGMs. This involves a series of experiments to test which material when coated will give the best results for adsorption. The methodology adopted in this work and the results obtained thereby from experiments conducted are discussed in the forthcoming sections.

Chapter 2 Literature review


There are various hydrogen storage methods viz. (1) gas storage, (2) liquid hydrogen, (3) solid storage (physisorption, metal hydrides, complex hydrides, chemical reactions). The most important criteria for deciding upon storage scheme are: safety, gravimetric and volumetric eciencies, cost, reversibility of uptake and release. Every technique listed above has one or the other limitations as follows:[4] Gas storage: 1. Low weight and volume storage eciency. 2. Signicant pumping losses above 55 MPa (8000 psi). 3. Safety concerns associated with high pressure gas storage.[5] Liquid hydrogen: 1. Liquefaction of hydrogen is relatively expensive. 2. Hydrogen being lost due to evaporation during dormancy and refueling must be captured or used. 3. Safety concerns associated with handling cryogenic liquids.[5] Solid hydrogen Hydride Storage: 1. Thermal management is required during charging and discharging hydrogen. 2. High system weight and low volumetric energy density (current technologies) compared to potential performance.[5] Surface Adsorbed Media Storage: 1. Low volumetric energy density. 2. Active cooling is required for operation and extended dormancy. 8

3. Heating is required to release hydrogen supply for use.[5] Complex Hydrides: 1. The complex hydride systems and chemical systems though have reasonably good eciency, reversibility of uptake and release of hydrogen is very poor.[4] Hollow glass microspheres (HGMs) are used as a medium of hydrogen storage which overcome above listed disadvantages besides meeting the important criteria for storage schemes mentioned above. Their intricate porous network with pores of size from 10 A to 1000 A[6] are comparable to the size of hydrogen molecules. Hence, HGMs are found widely in literature for use in hydrogen storage. Dalai et. al[7] have reported that HGMs have a leverage over other materials because of certain advantages such as light weight, low density, nontoxic nature, good mechanical strength, zero environmental pollution and low cost of production. HGMs are produced by pulverizing glass bottles to form ne free-owing powder with particle size of 1 140m[1], a wall thickness of 0.5 2.0m and a low density of 1.0 to 2.0gm/cc.[7] Various research articles have reported dierent compositions of HGMs like amber glass, borosilicate glass, etc. which have varying amounts of major elements like silicon, oxygen, sodium, boron and iron. In our work, amber glass has been selected for its known advantages over other materials. The high porosity and surface area of the HGMs provides a good diusivity and release rate for hydrogen gas at elevated temperatures. The maxium reported volume of hydrogen that could be stored in HGMs has been upto 150M P a which is higher than any other solidstate material accounting to high yield strength and volumetric eciency.[8] Albeit high storage capacity, HGMs are nonexplosive since each individual glass microsphere contains too small a volume of hydrogen gas to be dangerous, thus ensuring safety.[4] Apart from safe storage of hydrogen, HGMs are environmentally benign since they can be easily made from waste glass bottles which is why they can be termed as recycled materials. Moreover, their transportation is eortless since they have a very low density[9] thereby achieving a high energy by weight ratio in terms of storage. The above mentioned properties facilitate as a consequence a high potential for storage capacities upto 6-10 wt.%[10] However, the storage capacity varies greatly by the method of preparation, which consecutively is governed by factors like preparation temperature, ame length (in case of spheroidisation ), precursors (in case of sol-gel method), etc. Some of the most common methods of preparation are given below: (a) Acid etching of as-prepared HGMs[11] (b) Sol-gel preparation[12] (c) Precipitation method[13] (d) Flame spheroidization[7]

The prospect of using HGMs for gas storage at industrial levels would require an economic and large-scale route to produce spherical silica with high spheroidization eciency.[14] This criterion is satised by ame spheroidization since in this method formation of spheres is controlled by temperature and surface tension which a very high yield per gram of feed and cost-eciency. Therefore, this method is viable for large-scale industrialization. Once prepared, storage of hydrogen requires housing the HGMs in an isolated chamber with a certain amount of pressure and temperature causing lling of hydrogen into the volume of each individual microsphere. Furthermore, the need to measure temperature and pressure accurately during hydrogen adsorption has been reported by Blach et. al[15]. This they suggest, as a mandate, can be performed using an apparatus that is similar to Sieverts apparatus of which a schematic diagram is given below:

Figure 2.1: Schematic diagram of Sieverts appratus. An insightful view into adsorption on microporous substances such as HGMs elucidates as Dubinin[16] explains that a gas storage, in this case hydrogen, is caused by the presence of an adsorption eld in microporous structures and this happens in two stages, rst the gas is adsorbed onto the outer surface of the adsorbent and then diused through the porous bulk gradually lling into the volume of the material. This adsorption potential is determined by a function formulated by Polanyi: = RT ln ps /p where ps is the pressure of the saturated vapour of the adsorbate at a temperature T and p is the equilibrium pressure. This helps us revisit an earlier discussion that was made on the thermodynamic dependence of adsorption on HGMs. The presence of temperature and pressure values in the above equations is evidence that the processes of adsorption and diusion indeed are thermodynamic phenomena and control of said parameters is a must to achieve tangible results in adsorption. All the above mentioned characteristics, advantages, methods and phenomena interplay to help achieve one goal, that is viable application of HGMs in daily day life. Extensive research has till today found many major uses for HGMs and more are yet to come. However, currently the most important areas of application of HGMs are, 10

1. use as a light-weight ller for composite polymeric materials of dierent kinds; 2. creation of protective surface layers to prevent evaporation of toxic and highly volatile liquids (oil, petroleum products) 3. cryogenic technology; 4. fabrication of industrial explosives; 5. fabrication of acoustic and thermal insulating materials; 6. use as ller for paints and varnishes; 7. use as targets for laser thermonuclear synthesis; 8. fabrication of polymeric composites for electronics and electrical applications; 9. fabrication of abrasive materials; 10. dierent application in automobile industry ; 11. fabrication of abrasive articles -polishing cloths; 12. carbon dioxide storage in cryogenic technology; 13. containers for hydrogen storage; The above above sections have been a prelude to explain the reasons why hydrogen energy is important and why it is crucial to store them using hollow glass microspheres. Based on the literature review we in our work have adopted certain methods to demonstrate the same. This has been followed in the forthcoming sections.

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Chapter 3 Experimental
3.1 Preparation of glass frits:

The preparation of micron sized glass frits (pulverized glass) was done mechanically by using top-down approach. Waste glass bottles taken were washed to remove dust and other particulate impurities present inside and outside later left to dry. After drying the bottles were initially broken using a hammer into big chunks and eventually crushed into smaller pieces. These crushed pieces where then placed in a grinding machine that produced ne free-owing powder. The powder was continuously dried in an oven at a constant until usage. Before usage the frits were sieved and segregated into three dierent size ranges namely, 53 63m, 63 75m and 75 105m . However, the particles used for all samples were of the range since this provided the most optimum results in terms of yield.

3.2

Preparation of metal loaded HGMs:

Figure 3.1 represents the schematic diagram of a process called spheroidization which was used to convert glass frits into hollow glass microspheres (HGMs). As shown above, randomly sized frits were passed through a ame (stage I) produced by an airgas mixture at very high temperatures (approx. 2500 C), causing them to melt and form spheres due to surface tension (stage II). Followed by this the molten spheres were blown to a bigger size while forming a central cavity and pores through the walls before falling out of the ame to cooler temperatures resulting in solidication (stage III). This blowing eect was subsequent of the gases liberated from the metal salts added before spheroidization by soaking with the corresponding aqueous solution at dierent weight concentrations. The salts used were: (a) Cobalt nitrate hexahydrate (b) Zinc acetate hexahydrate (c) Magnesium nitrate hexahydrate 12

The nal product that resulted from spheroidization were perfectly spherical balloons with pores of varied sizes emerging onto the surface. Metal oxide coating were also identied during characterization, these were intended to enhance adsorption properties thermodynamically.

Figure 3.1: Schematic representation of spheroidization. Porous HGMs were then used for adsorption studies using an apparatus that is similar to the Seiverts apparatus of which images are given below:

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Figure 3.2: (a) Experimental setup for spheroidization. (b) Heating setup. All the samples were given a code based on percentage of metal doped and the metal salt used for loading, for example, ACo2 and HACo2, where A stands for Amber, H stands for HGMs, Co for cobalt and 2 for 2wt.%. Moreover, ACo2 indicates feed sample and HACo2 indicates product sample. A list of all product samples with their code, metal salt and percentage of loading have been listed below in Table 3.1 S. No. 1 2 3 4 5 6 7 1 2 3 4 5 6 1 2 3 4 Sample code HACo0.2 HACo0.5 HACo1 HACo2 HACo3 HACo5 HACo10 HAZn0.2 HAZn0.5 HAZn1 HAZn2 HAZn5 HAZn10 HAMg0.2 HAMg0.5 HAMg1 HAMg2 Metal salt loaded Cobalt nitrate hexahydrate Cobalt nitrate hexahydrate Cobalt nitrate hexahydrate Cobalt nitrate hexahydrate Cobalt nitrate hexahydrate Cobalt nitrate hexahydrate Cobalt nitrate hexahydrate Zinc nitrate hexahydrate Zinc nitrate hexahydrate Zinc nitrate hexahydrate Zinc nitrate hexahydrate Zinc nitrate hexahydrate Zinc nitrate hexahydrate Magnesium nitrate hexahydrate Magnesium nitrate hexahydrate Magnesium nitrate hexahydrate Magnesium nitrate hexahydrate Concentration (wt.%) 0.2 0.5 1 2 3 5 10 0.2 0.5 1 2 5 10 0.2 0.5 1 2

Table 3.1: List of metal loaded HGMs samples at dierent concentrations

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3.3

Characterization:

FTIR studies were carried out on feed and product to observe the dierences in the spectra and determine the possible reactions blowing agents undergo during spheroidization and also deduce the composition. FTIR on all samples were done using a Bruker Vertex 80 in the wavenumber range of 4000 400cm1 . The composition of all samples were conrmed through XRD, which was carried out using a Panalytical XPert Pro powder diractometer. The system was congured to use Cu K radiations between a scan range of 5 100 . Surface morphology of the microspheres were examined through FEG-SEM using a JEOL JSM-7600F at various magnications. However, the size, shape, yield and pores were studied through ESEM using a FEI QUANTA 200 also at various magnications. Images of the instruments are given below:

Figure 3.3: [From left to right] (a)FTIR system (b) XRD system (c) ESEM system

Figure 3.4: FEGSEM system

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Chapter 4 Results and discussion


4.1
4.1.1

Cobalt loaded samples:


FTIR studies:

Figure 4.1: FTIR spectra images for low and high concentration Cobalt loaded samples. Table 4.1 contains the peak assignment data of the IR spectra in Figure 4.1. The weight percent concentration of blowing agents used is 0.2, 0.5, 1, 2, 5 and 10 wt.% respectively.

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All samples show peaks in the 1050cm1 , 460 480cm1 and 770cm1 range. These correspond to the Si O Si anti-symmetric stretching, Si O Si bending and O Si O stretching respectively.[17] This conrms that the major phase of the sample is silica. Another signicant pattern is displayed by the peak at 1380cm1 corresponding to the symmetric stretching of N O bond.[18] It increases in amplitude with increment in blowing agent concentration. In addition, it is absent in the product samples which suggests the decomposition of cobalt nitrate hexahydrate during spheroidization. A very weak peak at 675cm1 appearing in most samples corresponds to the Co O stretching vibration.[19] This bond is present in Co3 O4 , which is one of the decomposition products of Co(N O3 )2 .6H2 O. The moisture coalesced, in both feed and product samples, produces a small blunt peak in the 3430 3480cm1 range and at 1620cm1 . These attribute to the O H stretching and H O H in-plane bending respectively. [17, 20]

4.1.2

XRD studies:

The XRD patterns of samples are shown in Figure 4.2. In the rst gure, the peaks represent two features and four features are observed in the second gure. The major feature is the amorphous nature of silica, represented by a broad peak around 2 of 1835 . This is found in all samples. The major feature is the evidence of the presence of cobalt nitrate shown by the peak at 2 = 29 .This is supported by three facts. First, this peak is found only in the feed (ACo0.2, ACo0.5, ACo1, and etcetera) and it increases in amplitude with increase in the blowing agent concentration. Second, the study of FTIR graphs also provides a similar pattern. Third, on referring to the highest peak values of JCPDS card no. 19-356, the 2 values were found to be matching. The next feature shows the presence of cobalt nitrate hexahydrate. This is found only in the high concentration samples. On referring to JCPDS card no. 251219 the peaks at 2 = 19 , 32 and 39 , 42 and 48 have found to be matching. The 17

fourth feature shows the presence of cobalt oxide. The peaks at 2 = 37 , 45 , 59 and 65 , have been matched with JCPDS card no. 9-418. This is only found in ACo10, which is the highest concentration sample.

Figure 4.2: XRD graphs for low and high concentration Cobalt loaded samples.

4.1.3

E-SEM:

E-SEM studies show the highly porous surface of microspheres. It was observed that the width and density of pores increase with concentration till it reaches a maximum at 2 wt.% and eventually decreasing in density with even higher concentrations (5 and 10 wt.%), however, pore width rather still increases. The initial increase in pore width and density is due to the increase in the number and cluster size of N O2 gas molecules that are liberated during spheroidization. However, a steep increase in the amount of surfaces depositions tends to block the smaller pores and leaving only sparse amounts larger pores, thus causing a decrease in pore density albeit increase in pore width. Traces of the patches of deposition that block the pores are observed been in Figure 4.3(c) and 4.3(d).

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Figure 4.3: ESEM images of cobalt loaded samples with (a) 0.5, (b) 2, (c) 5 and (d) 10 wt.% concentration.

4.1.4

FEG-SEM:

FEG-SEM images were recorded to conrm the formation of deposition on the surfaces of high concentration samples, although pores are not observed due to high electrostatic charging on the platinum coated surfaces. The rough patches can be clearly seen in Figure 4.4(b) and 4.4(c) which is evidential of formation of depositions. EDX results conrmed that these patches are composed of Co3 O4 .

Figure 4.4: FEG-SEM images of a) 3, b) 5 and c) 10 wt.% concentration. d) EDX image of 10 wt.% concentration.

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4.2
4.2.1

Zinc loaded samples:


FTIR studies:

Figure 4.5 shows the FTIR spectra of feed and product samples stacked together. The left image represents data of low concentration samples while the data on right is of high concentration samples.

Figure 4.5: FTIR spectra images for low and high concentration Zinc loaded samples. Table 4.5 given below represents the peak assignment data of the spectra shown in Figure 7, this is followed by an analysis of the given data. The silica present in all samples gives three signicant peaks. A broad peak in the 1030cm1 range, a medium-sized peak at around 480cm1 and a short peak in the 760cm1 range are majorly observed. They represent the Si O Si anti-symmetric stretching, Si O Si bending and O Si O stretching vibrations respectively.[17] The two small peaks in the 1400cm1 and 1600cm1 range are given by the symmetric and anti-symmetric stretching vibrations of COO group respectively.[21] This is supported by the fact that their intensity increases with concentration in the feed samples. Also, they are not found in the product since they thermally decompose to form CO2 gas. Another peak in the 640 680cm1 range, almost consistently appearing in feed samples is given by COO bending.[22] The moisture coalesced in all samples produces a small blunt peak in the 3420 3440cm1 region. This corresponds to the O H stretching.[20, 23] 20

4.2.2

XRD studies:

Results of powder diraction studies in Figure 4.6 show that in higher concentration samples the presence of slightly crystalline zinc acetate and oxide in the samples. The surface of the product however shows only presence of zinc oxide which is evidential of thermal decomposition of zinc acetate during spheroidization. The bump that appears in all samples at around 2 value of 22 is due to the amorphous phase composed mainly of silica. The peaks at 2 values 10 and 11 are produced by zinc acetate. [JDPS 1-89] All other peaks that appear in the range of 30 70 are produced by zinc oxide. [JCPDS 89-1397]

Figure 4.6: XRD graphs for low and high concentration Zinc loaded samples.

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4.2.3

ESEM:

Figure 4.7: E-SEM images of zinc loaded samples with (a) 0.5, (b) 2, (c) 5 and (d) 10 wt.% concentration. E-SEM images of zinc loaded samples are shown above. The pores are observed to initially increase in density but eventually decrease towards higher concentrations. The pore width however, remains unaected. This happens because as the concentration increases the smaller pores are blocked by ZnO depositions that also increase with concentrations.

4.2.4

FEGSEM:

Figure 4.8: FEG-SEM images of (a) 5 wt.% and (b) 10 wt.% concentration, (c) magnied patches of 5 wt.% and (d) 10 wt.% concentration. 22

FEG-SEM images conrm the formation of depositions on the surface of microspheres. Figure 4.8 shows these patches at higher magnication, clearly indicating an increase in the amount of deposition with concentration.

4.3
4.3.1

Magnesium loaded samples:


FTIR studies:

Samples of four dierent concentrations of 0.2, 0.5, 1 and 2 wt.% were characterized. Analysis of the data suggest the following details. As silica is the prominent compound in all the samples, three major peaks veried from literature[17] are associated with it. The Si O Si anti-symmetric is found to appear in the 1030cm1 range, Si O Si bending in the 480cm1 range and the O Si O stretching in the 760cm1 range. The presence of magnesium nitrate in feed is conrmed by the sharp peak in the 1380cm1 range appearing in all feed samples.[24] The small peak in the 650cm1 range is given by the M g O stretching.[19] Moisture drawn by the hygroscopic magnesium nitrate gives two peaks corresponding to bending and stretching in the 1640cm1 and 3430cm1 range respectively.[17, 20]

Figure 4.9: FTIR spectra images for low and high concentration Magnesium loaded samples. FTIR spectra images of magnesium loaded samples are shown above. Below given in Table 4.9 is the peak data assignment corresponding to the spectra shown in Figure 11. 23

4.4

Adsorption studies:

In all samples including cobalt, zinc and magnesium loaded HGMs 2 wt.% concentration showed the highest adsorption. This is attributed to the fact that at 2 wt.% the pore size and density are in optimum quantities. Below given are the images of adsorption graphs for cobalt, zinc and magnesium loaded samples respectively.

Figure 4.10: Adsorption graphs for cobalt samples. Figure 4.10 shows us that there is a rising trend in adsorption initially starting from HACo0.2 upto HACo2 and then there is decrease as the concentration is increased upto HACo10. The initial increase in adsorption is attributed to the increase in pore density from HACo0.2 to HACo2, also the bigger pores that are formed by larger molecules are partially blocked by the depositions which are in optimal amount to 24

form smaller pores thus increasing the adsorption potential. However, when we further proceed from HACo2 to HACo10, the amount of deposition increases rapidly causing most smaller pores to be blocked leaving only larger macro sized pores which allow hydrogen to escape thereby decreasing the amount of adsorption. The graph in Figure 4.11 illustrates this trend clearly:

Figure 4.11: Graphs showing the trend of adsorption values in cobalt loaded samples Besides cobalt loaded samples, magnesium and zinc loaded samples also show a similar trend and the fundamental phenomenon that causes this is the same. The graphs in Figure 4.12 and Figure 4.13 show the adsorption in zinc and magnesium loaded samples respectively. It can be observed from these graphs that regardless of the number of sample the behavior of gas adsorption remains same since the occurrence of pores and metal depositions follows the same trend. This behavior does not change in the samples we used because the major phase is of HGMs whose composition is same throughout and the only variation is in the metal salts. The corresponding images of the above discussion are given above.

Figure 4.12: Adsorption graphs for zinc samples.

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Figure 4.13: Adsorption graphs for magnesium samples.

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Chapter 5 Conclusion
The increasing dependence on Green energy has been the brainchild of various pioneering research work especially in the eld of material sciences. As a part the family of green resources, hydrogen energy has gained much importance not just in scientic paradigms but also in those political in nature. One of the must successful carrier and storage medium of hydrogen energy has been found to be hollow glass microspheres (HGMs). The work carried out by us builds around this idea and has utilized the potential of HGMs while the main theme being preparing and testing how metal loading onto the HGMs help enhance their adsorption properties. After carrying out a series of experiments we have come to the following conclusions. Hollow glass microspheres made from amber glass are most suitable for hydrogen adsorption. Before preparing HGMs, soaking the glass frits with metal salts enhances adsorption by making the surface conductive and thereby improving the thermodynamic eciency of the material. However, not all samples showed positive results but only those with 2 wt.% concentration of metal loading showed the highest amount of hydrogen adsorption. This was attributed to the fact that the pore density, pore width and amount of metal oxide deposition were at the optimum levels at the said concentration. Adsorption also varied by the temperature and pressure within the reaction chamber wherein a higher temperature of 200 and a pressure of 10bar increased the adsorption rate by an average of 55% as compared to the adsorption conducted at room temperature and 1bar pressure in the case of 2wt.%. Moreover, in order to achieve good adsorption the process of fabrication of HGMs has to be carefully selected, thus justifying our selection of ame spheroidization for production of HGMs. This process has provided better control than other processes known from literature on the deposition of metal oxide which is directly dependent on the concentration of metal loading. Further work in this direction is aimed at gaining better control over metal deposition and pore size by understanding the kinetics of gas/vapors molecules that are the principal agents responsible for pore and cavity formation. This is intended to result in higher adsorption and thereby allowing much higher lling of hydrogen into the volume of microspheres. Ultimately this would facilitate application of this technology at industrial level which would enable it to ease into everyday life of people consequently making our environment cleaner and safer. 27

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