STUDIES ON HYDROGEN CHEMISORPTION ON TITANIUM NANO POWDER

Dissertation submitted to KANCHI MAMUNI AR CENTRE !OR POST GRADUATE STUDIES "AUTONOMOUS# PUDUCHERRY$%&' &&( In Partia) !u)*i))ment o* t+e Re,uirements !or t+e a-ard o* t+e de.ree o*

MASTER O! PHI/OSOPHY IN PHYSICS 01

K2SUSAINATHAN
"Re.ister No3 454%4&6# Under t+e .uidan7e o*

Dr2 RAMADASS8 M2 S728 P+2 D2

(Research guide and Supervisor)

DEPARTMENT O! PHYSICS KANCHI MAMUNI AR CENTRE !OR POST GRADUATE STUDIES "AUTONOMOUS# PUDUCHERRY$%&'&&(

1 |Page

DEPARMENT O! PHYSICS8 KANCHI MAMUNI AR CENTRE !OR POST GRAGDUATE STUDIES8 "AUTONOMOUS#8 PUDUCHERRY$ %&' &&(2

Dr 2RAMADASS8 M2S728 2P+2D8 Asso7iate 9ro*essor8 De9artment o* 9+1si7s8 K2 M2 C2 P2 G2 Studies "Autonomous#8 Pudu7+err1 $ %&' &&(2

0ONA!IDE CERTI!ICATE
This is to certify that the dissertation titled :STUDIES ON HYDROGEN CHEMISORPTION ON TITANIUM NANO POWDER submitted to KANCHI MAMUNI AR CENTRE !OR POST GRADUATE STUDIES "AUTONOMOUS#8 PUDUCHERRY is a bonafide research work carried out by Mr2 K2 SUSAINATHAN "Re.ister
No3 454%4&6# for the award of the degree of MASTER O! PHI/OSOPHY IN PHYSICS

under my guidance and supervision during the requisite period. This work is original and entirely carried out by the candidate for the fulfillment of the project work. I also certify that this research work has neither formed the basis for the award of any other Degree, Diploma, ellowship or any other similar titles of the any university or institution. This is also to certify that the dissertation represents the independent work of the candidate.

Dr2 RAGURAMAN !ead and "ssociate professor

Dr2 RAMADASS "ssociate professor

DIRECTOR P)a7e3 Pudu7+err1 Date3

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Shri. C. Ramesh., Materials Chemistry Division, Chemistry Group, Gan hi Centre !or "tomic Research, Kalpakkam#$%&'%(.

Place : Kalpakkam Date : In ira

)*+",ID- C-R.I,IC".-

This is to certify that the project work titled /S.0DI-S *+ 12DR*G-+ C1-MIS*RP.I*+ *+ .I."+I0M +"+* P*3D-R4 submitted to the K"+C1I M"M0+I5"R C-+.R- ,*R P*S. GR"D0".- S.0DI-S 6"0.*+*M*0S7 for the award of the degree of Master o! Philosophy is a bonafide record of the research work done by Mr. K. S0S"I+".1"+, Re8. +o. ('($(%9, Department of Physics, Kanchi Mamuni ar !entre "or Post #raduate $tudies, Puducherry%&'('') under my guidance and super ision at the M".-RI":S C1-MIS.R2 DI5ISI*+, C1-MIS.R2 GR*0P, I+DIR" G"+D1I C-+.R- "*R ".*MIC R-S-"RC1, K":P"KK"M# $%&'%( during the period "ebruary 2'1* to +ugust 2'1*,

Mr. C. R"M-S1 Scienti!ic *!!icer;G

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DEPARMENT O! PHYSICS8 KANCHI MAMUNI AR CENTRE !OR POST GRAGDUATE STUDIES8 "AUTONOMOUS#8 PUDUCHERRY$ %&' &&(2

Mr2 K2SUSAINATHAN8 M2 P+i) Resear7+ S7+o)ar8 De9artment o* 9+1si7s8 K2 M2 C2 P2 G2 Studies "Autonomous#8 /a-s9et8 Pudu7+err1$ %&'&&(2

DEC/ARATION

I hereby declare that the dissertation titled :STUDIES ON HYDROGEN CHEMISORPTION ON TITANIUM NANO POWDER; is a record of project work done by me for the degree of Master o* P+i)oso9+1 in 9+1si7s under the guidance of Dr2 RAMADASS, Asso7iate Pro*essor8 Kan7+i Mamuni<ar Centre !or Post Graduate Studies "Autonomous#8 Pudu7+err1, and the work has been carried out at Indira #andhi centre for "tomic $esearch, %alpakkam, and it has not been submitted for the award of any Degree, Diploma, ellowship of any other &niversity or Institutions.

P)a7e3 Pudu7+err1 Date3

'K2SUSAINATHAN# M2 P+i)228 S7+o)ar2

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"ckno<le 8ements
The successful completion of my project work would be incomplete without mentioning the people who ga e me constant guidance and encouragement throughout, "irst of all, . record here my happiness in thanking the almighty for bestowing me with knowledge and courage which guided me all along during the course of my project work, . wish to e/press my sincere gratitude and indebtedness to my parents for their blessing, sisters an other !amily mem=ers for their lo e and support to me, .t is ery grateful to thank my 1*D Dr. V. Raguraman Associate Professor, Department of Physics, K.M.P.C.P.S, Pondicherry who has gi en me a moti ation and encouragement throughout the period of this project work, .t is also my great pleasure to thanks Dr,*. P. S12M" Director of K,M,P,!,P,$, Pondicherry, who has gi en me the opportunity to do the project at .#!+0, . e/press my heartfelt gratitude to Dr. P.R. Vasudeva rao Director, IGCAR , Dr. K. agara!an. Associate Director, chemistry Group, Dr.K.V.". Kutty, Head, Materials chemistry division, Dr. S. Anthonysamy, Head, Materials processing and characterization section, Dr.M.Sai#a#a Associate director, Resources Management Group IGCAR who had allowed me to carry out my project work and pro iding the necessary facilities, . would like to e/press my profound gratitude and deep regards to my internal guide Dr. R.Ram ass +ssociate Professor, Department of Physics, K,M,P,!,P,$, Pondicherry, for his guidance, enthusiastic super ision, technical discussions, kindness and patience throughout the period of this project works

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. wish to record my deep sence of gratitude and sincere thanks to my research guide shri C.Ramesh scientific officer material chemistry section, chemistry group .#!+0 kalpakkam, for his unstinted inspiration, in aluable guidance, encouragement, keen interest, good wishes and aluable suggestions throughout my entire research tenure, . am also grateful to him for critically re iewing this thesis,

.t gi es me immense pleasure to acknowledge to my research co%guide shri +.muru8asan, scientific officer, material science section, and chemistry group .#!+0 kalpakkam, for critically e aluating my research acti ities time to time and also for pro iding the laboratory 1 computational facilities and se eral aluable suggestions for completion of this work . e/press my sincere thanks to Mr, > Mrs. Mathan, Chan ra mo8an, Shamima 1ussian , helping me for recording the ? @ray i!!racto8ram, )-. sur!ace area measurement , S-M ima8e and many useful suggestions pertinent to this dissertation, . would like to carry my thanks to my professor Dr. Guptha, Dr. Rama=ramam an Dr. Meenakshi Associate Professor, Department of Physics, K.M.P.C.P.S, Pondicherry gi en me a support , .t is a great pleasure to acknowledge my 2ab mates Mr."!iAith !or helping me and pro iding kind supports and encouragement during my research work, . am also thanks to all my chemistry ivision collea8ues an sta!! mem=ers for their support at different times, 2ast but not least . want to say thanks to my friends Mr. $amilselvam, Mani%andan stand with me at all the cases and thanks for their lo ingness,
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"inally, . am e/tremely thanks to all those people who were the pillar of support to me,

*RG"+IS".I*+ *, .1- DISS-R.".I*+ C1"P.-R#I

.3T04D5!T.43 This chapter contains the basic information about hydrogen demand, hydrogen economy, hydrogen production methods, hydrogen storage methods and hydrogen storage target which forms an aim of research in my project,
C1"P.-R#II

:iterature revie<
+ re iew of literature on hydrogen chemisorption on titanium and its applications
C1"P.-R#III

Theory of chemisorption and physisorption

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.n this chapter theory of chemisorption, features of chemisorption, a sorption Kinetics in !lo< metho , theory o! Physisorption are C1"P.-R#I5 iscusse issociation chemisorption an

-Bperimental techniCues
The e/perimental techni7ues for hydrogen chemisorption on titanium powder sample using TPD04 instrument are discussed, The samples were analy8ed by 9%ray diffraction, $canning electron microscope, :;T techni7ue etc, The details of the e/perimental techni7ues are gi en in this chapter
C1"P.-R#5

-Bperimental
Details of e/periments carried out using TPD04, 9%ray diffraction, $canning electron microscope, :;T are discussed,

C1"P.-R#5I

Result an

iscussion

The results obtained in the arious studies carried out are presented in this chapter and discussed,
C1"P.-R#5II

Summery an

conclusion

The outcome of the present work and its significance for future studies are consolidated in the summery and conclusion,

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!hapter%1 I. IN R!D"C I!N

.,1, #eneral :ackground
!i ili8ation of society demands high per capita consumption of power, !ontinuing growth in global population coupled with the rapid pace of industriali8ation in +sia suggests that the number of light duty ehicles is use worldwide will almost triple #y $%&% '(). As today*s vehicle +leet is #ased almost entirely upon the internal com#ustion engine, the transportation sector is highly dependent on petroleum derived +uels, in INDIA appro-imately $./ o+ petroleum consumption can #e attri#uted to #e used in transportation'$). Conse0uently, transportation is a signi+icant source o+ car#on dio-ide emission. In order to sta#ilize glo#al C! $ levels and simultaneously meeting the mo#ility needs o+ a gro1ing population, the

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development o+ ne1, environmentally sustaina#le technologies +or personal mo#ility is essential '/). ;nergy is one of the most important topics in the 21st century, =ith the rapid increase in en ironmental pollution and e/ploitation of fossil energy resources, there is a high demand for renewable and clean energy sources that can replace fossil fuels to support the sustainable de elopment of the global economy and society, $e eral new types of clean energy sources, such as wind, solar, hydro, geothermal, and biomass ha e recei ed worldwide concern and increased research interest due to their properties being sustainable, clean and en ironmentally friendly, >owe er, for the en ironmentally friendly use of the energy produced by these sources in final application, a clean, efficient, and safe carrier is necessary ?-@, The drawbacks of renewable energies such as wind, solar etc, are that they are intermittent sources, The wind turbines do not produce the same amount of electricity all the time as wind power falls as wind speed reduces, The same way solar power generation also aries with intensity of sunlight and drops to 8ero at nights and when the atmosphere is cloudy, #eneration of hydrogen by means of electrolysis of water using the abo e renewable sources and storing by suitable method is considered to be one of the best methods, The stored hydrogen can be used in the fuel cell for production of power and a schematic of the scheme is shown in fig ?1@,

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&igure'( hydrogen production, storage and usage in day today life

>ydrogen based fuel cells technology is #eing pursued as an alternative to gasoline +or internal com#ustion engine as an energy carrier +or use in vehicle. he advantages, it has the highest energy density #y 1eight compared to any common +uel that can #e produced rene1a#ly +rom a variety o+ +eed stoc2s 'non3+ossil) and 1hen com#ined 1ith o-ygen in a proton e-change mem#rane '45M) +uel cell it can #e used to generate po1er 1ith only 1ater as a #y3product '&). 6o many countries are serious on this research to store hydrogen in di++erent materials in di++erent 1ays. he ".6 +ocus to developing vehicles that achieves +uel economies o+ 7%.& 2m.2g H $ 'e0ual to $(.$2m.8 gasoline on an energy e0uivalence #asis) 1hich is 7/9
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higher than the +uel economy +or the gasoline':), #ut there is a pro#lem +or hydrogen storage due to lo1 volumetric density resulting high coast.

.,2 >ydrogen economy

>ydrogen is the most abundant element on earth, but less than 1A is present as molecular hydrogen gas, >2, The o erwhelming majority is chemically bounded as >24 in water, and some are bound to li7uid or gaseous hydrocarbons, $ince water is the only by%product when hydrogen is burnt, >2 can be considered as a clean form of energy on the global scale ?6@, + clean way to use hydrogen as fuel therefore can be en isioned as a linked network of chemical processes that produce hydrogen through electrolytic, photolytic, or thermochemical splitting of waterB store hydrogen chemically or physicallyB and con ert the stored hydrogen to electrical energy and heat at the point of use, This is what is meant by the term Chydrogen economyD, which effecti ely addresses the major challenges of the 21st century ?), <@, The push towards the hydrogen economy began in the 1<6's when the international association for hydrogen energy was formed, which represents a isionary for future energy stream, +s shown in fig,2, The ision of an energy stream originates in the sun, flows through hydrogen as a carrier to perform electrical work, and produces water as its only by%product,

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&igure)( the hydrogen cycle

:efore the hydrogen economy can become a reality, howe er, grand technical challenges must be o ercome in each one of the three functional areasB production, storage and use, in which the main drawback in proceeding with the hydrogen economy is hydrogen storage, particularly for mobile application ?1', 11@, "or e/ample, fle/ible use of hydrogen as a carrier of energy re7uires a means to store e/cess of > 2 produced for later use, to transport stored hydrogen from the point of production to the point of use, and to charge and discharge hydrogen con eniently from the storage container according to need,

.,* >ydrogen Production Methods

Many production processes for hydrogen e/ist, The hydrogen can be produced from the fossil fuels ?e,g,, steam reforming of natural gas or other light hydrocarbons, gasification of coal and other hea y hydrocarbons@ or water ?electrolysis of water, direct and indirect thermochemical decomposition, and processes dri en directly by sunlight %photo catalytic route@, +lthough ha ing so many choices of resources sounds complicated, but indeed it is a great ad antage, because no one region or country has to be dependent on one resource to produce hydrogen and whiche er resources are suitable en ironmentally and economically can be used, .n an
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en eloping country like .ndia, by means of hydrogen economy, we can ha e decentrali8ed energy, as many remote areas are not ha ing access to electricity?12@, Presently, the commerciali8ed hydrogen production processes are mostly fossil fuel based, like, steam methane reformation, partial o/idation of methane, auto%thermal reforming and coal gasification E the cheapest and largest being generated by steam%methane reformation, Though all these processes generates !42, !42 generated from the reformation process is highly concentrated, therefore the reco ery is much cheaper than the diluted e/haust gas of the fossil fuel, :ut the main ad antages of hydrogen economy comes if hydrogen is e/tracted from water, using !42%free primary sources of energy such as solar energy, wind energy, or nuclear energy?1*, 1-@, The different production methods of hydrogen from water are described in the following section,

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$a#le'( Different hydrogen production methods, *here hydrogen is Method Process "eed $tock ;nergy ;mission !arbon se7uestration can mitigate its small emission $mall emission, !arbon $e7uestration can mitigate it $mall emission, !arbon se7uestration can mitigate it 3o ;mission

$team 0eformation

3atural #as !oal, :iomas s

>igh temperature steam

!oal #asification Thermal

$team and o/ygen at high temperature 1 pressure Moderately high Temperature steam =aste heat from high temperature nuclear reactor ;lectricity from wind, solar, hydro, nuclear ;lectricity from direct sunlight Direct $unlight >igh temperature heat >igh temperature heat

Pyrolysis

:iomas s

Thermochemical =ater $plitting

=ater

;lectrolysis ;lectrochem ical

=ater

3o emission

Photo electrochemical Photo biological

=ater =ater 1 +lgae :iomas s :iomas s

3o emission

3o emission $mall emission $mall emission

:iological

+naerobic "ermentati e Micro organism

produced from *ater

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.,*,1 >ydrogen production from water

>ydrogen generation from water can be depicted by the following e7uation

1(* DDDDE 1( F ';( *(

The reaction is highly endothermic '! ( )*+ %,mole-. at )/0 %1, and for direct thermolysis of water, a very high temperature is required '2)344 561. The energy required to split water can be provided by a primary energy source, like, solar, wind, nuclear heat or by a secondary energy source like electricity or a combination of these sources using a chemical process. 7o, a large collection of diverse processes are involved for hydrogen generation from water and some of which are listed in Table.. 8one of the above processes e9cept electrolysis has been commerciali:ed and although electrolysis is an established process, cost of hydrogen production is very high. 7o, efforts are being taken to improve efficiency and to minimi:e cost of these processes to make them commercially viable. Thus, $;D on various aspects like material development, catalyst development, reactor design etc. has to be carried out

.,- Hydrogen storage methods

.n principle, hydrogen can #e stored either in a physical form +gas or li,uid- or chemical form '(&). hydrogen are discussed #elo1. he methods #eing used to store

I.;.( 8i0uid hydrogen storage 'Cryostorage)

2i7uid hydrogen storage is currently the bulk hydrogen storage medium of choice and has a ery impressi e safety record, 5nfortunately, the energy re7uirements o+ li0ue+action are high, typically /%9 o+ the hydrogen*s heating value. 8i0uid hydrogen 1ill remain the main techni0ue o+ #ul2 and stationary hydrogen storage +or the +oreseea#le +uture '(:).
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The hydrogen can also be stored as a li7uid in a cryogenic tank at ambient pressure and low temperature ?%2(2oc). Hydrogen stored as a li0uid has a relatively high volumetric density '<%.7=g.m /). In+rastructure pro#lems are three +old> +irst, the li0ue+action process is costly. 6econd, small scale li0uid hydrogen production is impractical. hirdly, lo1 volume distri#ution.dispensing o+ li0uid hydrogen are e-pensive '(<).

.,-,2 Compressed gaseous hydrogen storage

.t is feasible to store hydrogen in #aseous form, >igh pressure gas cylinders can store hydrogen at a pressure of 2' MPa and storage is e en possible up%to pressure of )'MPa in newly de eloped light weight composite cylinders where the hydrogen olumetric density can reach -'KgFm *, $ince the hydrogen gra imetric density is low, there are also problem in holding the high pressure, especially in the regions with high population density, !ompressed gaseous hydrogen containers consisting o+ /;.& mpa '&%%% psi) '/;$ atmospheres) gaseous hydrogen in metal or plastic lined car#on +i#re 1ound pressure vessels o++er advantages +or storage. 6implicity o+ design and use, high hydrogen +raction, rapid re+ueling capa#ility, e-cellent dormancy characteristics, minimal in+rastructure impact, high sa+ety due to inherent strength o+ the pressure vessel, and little to no development ris2 are evident advantages. he disadvantages are system volume, use o+ high pressure, integrating the automotive designer etc. Compressed gas storage is supporta#le #y small3scale hydrogen production +acilities as 1ell as large scale hydrogen production +acilities. hus a possi#le hydrogen in+rastructure transition path1ay e-ists. ?or these reasons, room temperature compressed gas storage is vie1ed as the most appropriate +uel storage system +or 45M +uel cell vehicles '(7).

.,-./ 4hysical storage on high sur+ace area materials

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@ased on 1ea2 van der Aaals interaction #et1een gas molecules and solids, hydrogen molecule can #e reversi#ly stored on high sur+ace area materials such as car#on #ased materials, zeolits structures, and metal organic +rame1or2 materials, respectively. Ho1ever, the amount o+ hydrogen that can #e adsor#ed on porous materials at am#ient temperature and high pressure are much lo1er '%.&1t 9). materials lies in their ready reversi#ility. he advantage o+ the sor#ed his is also their largest

disadvantage. Ho1ever, as they contain hydrogen #y means o+ 1ea2 4hysisorption +orces 'Bander Aaals), lo1 temperatures '3(C: %C) and high pressures are re0uired +or signi+icant adsorption '(C).

.,-.; Metal Hydride storage method

Metal hydrides can be subdi ided into two categoriesG low dissociation temperature hydrides and high dissociation temperature hydrides, The low temperature hydrides suffer +rom lo1 H$ +raction ' temperature hydrides re0uire a heat source to D $9). he high the high generate

temperature o+ dissociation ' D /%% !C). @oth systems o++er +airly dense H $ storage and good sa+ety characteristics. Indeed it is the #ad characteristics o+ dissociation 'high temperature, high energy input) that create the good sa+ety characteristics 'no or slo1 H$ release in a crash). ?or vehicular hydrogen storage, metal hydrides are either too heavy or their operating re0uirements are poorly matched to 45M vehicle systems. Aithout a dramatic #rea2through achieving high 1eight +raction, lo1 temperature, lo1 dissociation energy, and +ast charge time, metal hydrides 1ill not #e an e++ective storage medium +or 45M +uel cell vehicles. ?or stationary storage, the 1eight o+ metal hydride system is not an adverse +actor. Conse0uently, their attri#utes o+ high volumetric storage density and sta#ility ma2e them 0uite attractive. Improving resistance to gaseous contaminants and

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increasing system cycle li+e remain as o#stacles to #e overcome. It stores hydrogen #y chemically #onding the hydrogen to metal or metalloid elements and alloys '+ig;). Hydrides are uni0ue #ecause some can a#sor# hydrogen at or #elo1 atmospheric pressure, then release the hydrogen at signi+icantly higher pressure 1hen heated and there is a 1ide operating range o+ temperatures and pressures depending on the metal and alloy chosen. 5ach metal and alloy has di++erent per+ormance characteristics, such as cycle li+e and heat o+ reaction '$%).

&igure.( Schematic o! a Metal 1y ri e # hy ro8en is inserte atoms in a soli

in =et<een the

.,( >ydrogen storage target

The current goal is to de elop an effecti e on%board hydrogen storage system for mobile applications, .n order for hydrogen powered ehicles to be competiti e with comparable ehicles in the market place, the on%board hydrogen storage system needs compact, light, safe and affordable containment and should co er a dri ing range of -'' km, ) kg of hydrogen is needed for the combustion engine ersion in comparison to - kg hydrogen for an electric car with a fuel cell, +t room temperature and atmospheric pressure, -kg of hydrogen gas occupies a olume of -(m *, which is hardly a practical solution for a ehicle ?21@, >igh%pressure hydrogen cylinder, olumetric density, and therefore is now
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li7uefied hydrogen tank, and solid metal hydride are possible options, $olid metal hydride has the largest

considered a more safe and effecti e way to handle hydrogen than compressed gas and li7uid hydrogen, The hydride offers olumetric hydrogen densities substantially greater than that of compressed gas and is comparable to or e/ceeding that of li7uid hydrogen, >igh pressure containment essels or cryogenic tanks ?1@ are not re7uired for solid metal hydride storage,

&igure/( $he gravimetric storage capacities of hydrogen in different form

.n 2''< the 5$ Department of energy ?5$ D4;@ updated the hydrogen storage system performance targets for light duty following criteria for the hydrogen storage transportation were setG >igh >2 storage capacity ?(,(wtA> for system@ Moderate operation temperature for hydrogen release and uptake, ideally between &'%12''!, "a orable kinetics for hydrogen absorptionFdesorption, ehicles ?22, 2*@, The suitable for technology

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2ow cost 2ow to/icity and non e/plosi e,

The 5$ D4; hydrogen storage system targets help guide researchers by defining system re7uirements in order to achie e commercially efficient storage for mobile application ?fig -@ !onsidering these facts, the hydrogen storage using metal hydride is the best method, iable hydrogen storage capacity, reaction enthalpy, and reaction kinetics for

'.$ Research aim an

scope

Present fossil fuel based energy system has drawbacks of polluting en ironment by releasing green house gases, .n the recent past, 0 1 D on fuel cell based energy system are gaining momentum like in the areas of catalysts, proton conductors and hydrogen storage materials, .n sodium cooled fast reactors, large 7uantities of hydrogen are released during arious processes, There is need to find suitable hydrogen storage material for trapping the hydrogen released from such processes, +lthough there are so many substantial research and de elopment acti ity in the field of hydrogen storage materials, none of the materials studied to date has demonstrated sufficient hydrogen storage capacity or efficiency at the re7uired operating temperature range, There is still considerable opportunity for study of new materials or material systems that could fulfill all the re7uirements for efficient hydrogen storage for mobile applications, =ith regards to the e/isting materials or material systems research is still needed to impro e the chemisorptionFdesorption performance and understand the mechanisms of chemisorption and desorption reactions with or without effecti e catalyst doping, Therefore the research interest is turned to the light metal titanium due to its high olumetric and gra imetric storage capacity, >owe er, use of
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this metal for hydrogen storage is challenging because the stability of a metal hydride must lie within a specific range for the chemisorptionFdesorption boundary at pressure and temperature that is usable in practical application, The primary aim of this research is to promote the light metal such as titanium for hydrogen storage, The e/periment is done using TPD04 instrument for hydrogen uptakeFrelease studies, The samples were characteri8ed by 90D for structural information, $;M for morphology and :;T for surface area measurement,

Chapter#II
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:iterature revie<
&elicia et alG 0eported that the titanium beds are the safety stone and transport hydrogen isotopes, particularly for tritium, The isotopes of hydrogen that can be stored on titanium bed and they are stable and may be remo ed with e/perimental ery high purity with an appropriate treatment, for this they essel they loaded with 2'g of titanium powder as a bed and made an new e/perimental step for hydrogen storage an titanium bed, .n the then the e/perimental essel is heated up to &'' o! in acuum for 2 hrs, +fter the acti ation process is o er the titanium powder bed was cooled slowly down to 26o!, +fter the process is completed hydrogen is e/posed to the titanium bed at 2- bars, The reaction between hydrogen and titanium is ery e/othermic once the reaction is o er 2- bars is reduces to )bars from this they found that the reaction is take place finally they concluded that the storage of hydrogen isotopes on titanium beds could be considered as a suitable and safe method, The properties of titanium hydride suitable for hydrogen storage include the ability to bind isotopes at normal temperature and pressure, and also being easily prepared, reaction is spontaneous at room temperature and the only re7uirement is acti ation process due the presence of the o/ide layer at titanium powder, P.cremaschi et alG 0eported that the chemisorption of hydrogen on titanium is treated using an ab initio !. theory for the surface region, The reacti ity of transition metals with hydrogen has been the subject of numerous e/perimental studies, .n this work they consider the theoretical treatment of the adsorption and dissociation of hydrogen molecules on a titanium surface using an electronic theory that permis the accurate computation of molecule solid surface interactions, This theory is based on a many electron approach in which configuration interaction calculations are performed at an ab initio le el at the adsorbent and surface region by this
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reaction they finally concluded that the hydrogen?> 2@

adsorption an a

titanium ?Ti@ surface are considered, The hydrogen orbital locali8ation and the surface adsorption site in the remainder of the electron distribution of the lattice modeled as a large cluster and a simplified treatment of hydrogen%titanium dissociation of hydrogen significantly abo e surface predicted and the crystal structure for titanium ?Ti@ is he/agonal closed pack after the reaction is o er the it changes is crystal structure to "ace center cubic for titanium hydride ?Ti>2@ 0ugo ricarda 1schommler et alG 0eported that there are many different allotropic forms for titanium hydride such as H, I, J%phases depending on the hydrogen concentration temperature and applied pressure, .n that at below &'' K J%phases is commonly found when Ti is e/posed to pure hydrogen, for smaller hydrogen concentration it has been obser ed a phase transition to H%phase and the I%phase which appears at higher temperatures, they taken 9%ray diffractogram obtained for Ti>2 powder used in the in estigation from that the reflections could be inde/ed as belonging to the H%phase and lattice parameter is found to be aK-,-(& + o, the T#+ result for titanium shows the total initial amount of hydrogen in the hydride powder was found to be close to 2,<1L% ',1&wt it is corresponding to a composition of about &' A and their must be wt loss in the sample this is due to heating rate, and the 9%ray results of H%phase 2u 3iang,ing et alG 0eported a study on hydrogen absorption and desorption properties of titanium under an initial hydrogen pressure of ',2(mpa at different temperature was fulfilled the hydrogen absorption rate constant k alue is 6,*&-M1' %*Fs under an initial hydrogen pressure of ',2(mpa at 66*K , The depth profile of hydrogen in titanium was performed by secondary ion mass spectroscopy the relati e hydrogen content is in ariable between about 6''nm and 12('nm in titanium, The 9% ray diffraction and scanning electron microscope studies on titanium hydrogen were performed, and the hydrogen absorption rate constant K ale is

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6,*&-M1'%*Fs in titanium under an initial hydrogen pressure of ',2(mpa at 66* K, the desorption pressure of titanium hydride is <1pa at 66*K after heating for (-'' sec and from the result of 9%ray diffraction concluded that the titanium has an crystal structure of face center cubic 4illiams.D. et al( 0eported a study of factors affecting the reaction

between titanium and hydrogen gas at ambient temperature between 6( o" and 1*'o", this reaction is fa ored by ultra high purity hydrogen, This is done under ail acuum annealing to dissol e surface o/ides and increased hydrogen pressure for storage on titanium, They are purchased the titanium alloys from a commercial supplier, unalloyed Ti, Ti%(+l%2,($n, Ti%&+l%-N and Ti%1*N%11!r%*+l and the reaction studies were made in two types of e7uipment, one for low%pressure studies and one for high pressure studies, .n this paper they said that a reaction between hydrogen gas and titanium to form titanium hydride is possible at room temperature as a result, small difference in e/perimental techni7ue can pre ent a reaction where one is normally e/pected or cause a reaction where none is e/pected, $e eral factors were found the occurrence of a reaction these included increased hydrogen pressure, .ncreased reaction temperature, abrasion of the titanium surface immediately before e/posure to hydrogen :ased upon the studies performed during this program, the use of titanium alloys in a hydrogen atmosphere at room temperature must be approached with caution, + hydrating reaction can occur and in certoin cases can process 7uite rapidly causing se ere piting ar con ersion of major amounts of materials to hydride,

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!>+PT;0%... ...,1 +3 4N;0N.;= 4" T.T3+.5M

Titanium, Cthe space age metalD, is the chemical element with atomic number 22 and symbol Ti, .t is a transition metal with sil er color.

...,1,1 >istory of Titanium

Titanium was first identified as a metallic element by #regor in ;ngland in 16<1, .n 16<(, Klaproth, a #erman chemist, redisco ered this metal and named it titanium, after the Titans, the powerful sons of earth in #reek mythology '$;). he element i is the ninth most a#undant metal in the planet and +ourth most a#undant structural metal a+ter aluminum, iron and magnesium. It occurs 1ithin a num#er o+ mineral deposits, principally Rutile +$i5)- and 6lmenite +&e$i5.-, 1hich are 1idely distri#uted in the 5arthEs crust 'a#out %.:9) and lithosphere. It is also +ound in almost all living things, roc2s, 1ater #odies, and soils. he metal is e-tracted +rom its principal mineral ores via the Kroll process or the 0unter process. Its most common compound, titanium dio-ide, is used in the manu+acture o+ 1hite pigments

...,1,2

Properties

...,1,2,1 Physical Properties ?2(, 2&@G

2& | P a g e

+ metallic element, titanium is recogni8ed for its high strength%to% weight ratio,

The relati ely high melting point ?o er 1,&-< O! or *,''' O"@ makes it useful as a refractory metal,

.t is fairly hard, non%magnetic and a poor conductor of heat and electricity,

Machining re7uires precautions, as the material w ill so+ten and gall i+ sharp tools and proper cooling methods are not used. 8i2e those made +rom steel, titanium structures have +atigue limits 1hich guarantees longevity in some applications.

he metal is a dimorphic allotrope 1ith the he-agonal alpha +orm changing into the #ody3centered cu#ic 'lattice) F +orm at 77$ GC '(,:$% G?).

he speci+ic heat o+ the alpha +orm increases dramatically as it is heated to this transition temperature #ut then +alls and remains +airly constant +or the F +orm regardless o+ temperature.

Titanium is only weakly attracted to the magnet. It is not a good conductor o+ electricity and heat. metal at elevated temperatures. ;%%oC. itanium can catch +ire and cause his is 1hat limits its application in severe damage in the circumstances 1here it is ru##ed against 1ith harsh environment to region 1here the temperature does not e-ceed

...,1,2,2 !hemical Properties

26 | P a g e

The most noted chemical property of titanium is its e9cellent resistance to corrosion< it is almost as resistant as platinum and capable of withstanding attack by acids, moist chlorine in water but is soluble in concentrated acids.

This metal forms a passive and protective o9ide coating 'leading to increased corrosionresistance1 when e9posed to elevated temperatures in air, but at room temperatures it resists tarnishing. =hen it first forms, this protective layer is only .>) nm thick but continues to grow slowly reaching a thickness of 25 nm in four years duration.

Titanium burns in air when heated to 1,200 C (2,190 ! and in "ure o#ygen when heated to $10 C (1,1%0 ! or higher forming titanium dio#ide. &s a resu't, the meta' cannot be me'ted in o"en air as it burns before the me'ting "oint is reached. (o me'ting is on'y "ossib'e in an inert atmos"here or in a )acuum. *t is a'so one of the few e'ements that burn in "ure nitrogen gas (it burns at +00 C or 1,,-2 and forms titanium nitride, which causes embritt'ement!.

?9periments have shown that natural titanium becomes radioactive after it is bombarded with deuterons emitting main'y "ositrons and hard gamma rays.

=hen it is red hot, the metal combines with o9ygen, and when it reaches 334 56 '.,4)) 5 1 it combines with chlorine. It also reacts with the other halogens and absorbs hydrogen.

...,1,2,* #eneral Properties

PROPERTIES TITANIUM

?26@

PROPERTIES

TITANIUM

&tomic number &tomic weight &tomic )o'ume Co)a'ent radius Transformation tem"erature *oni1ation "otentia' Therma' neutron absor"tion cross

22 ,-.90 10.$,cm%0mo' 1.%23& ++2 3C $.+2+26 5.$ barns0atom

.eat of fusion .eat of )a"ori1ation ("ecific gra)ity .ardness 2icro hardness Tensi'e strength 8oung9s modu'us

,,0 k/0kg 9.+% 2/0kg ,.5 -0 to-, .45 2-%.6 2,027a 120:7a

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section Co'or &'"ha (<++2.53C, Crysta' or 1$203 ! (tructure 5eta (=++2.53C, or 1$203 ! ;ensity 2e'ting "oint (o'ids 0'iCuids 5oi'ing "oint ("ecific heat (at 253C ! Therma' conducti)ity

;ark gray .e#agona' C'osed "acked 5ody centered cubic ,.50$g0cm% (0.1$%'b0in%! 1$$+@10 3C (%0%5 3 ! 1-253C (%1%5 3 ! %2$0 3C (5900 3 ! 0.522% k/0kg0 ? 11., E0m. ?

7oison9s ratio &t ,0m0min Coefficient (125ft0min! of &t %00m0min friction (1000ft0min! Coefficient of 'inear therma' e#"ansion A'ectrica' conducti)ity A'ectrica' resisti)ity (at 203C! A'ectro negati)ity Tem"erature coefficient of e'ectrica' resistance 2agnetic susce"tibi'ity ()o'ume, at room tem"erature!

0.%$1 0.+ 0.$+ +.,1>m0m. ? %B*&C( (Cu is 100B! ,20nD.m 1.5, "ou'in9s 0.002$0 3C 1+0(@1.-!F10G$

$a#le )( Properties of $itanium

...,1./ ?acts and #ene+its o+ itanium

'$<)

>

.t has highest strength%to%weight ratio of any metal, .t is as strong as steel, but -(A lighter,

.ts cost is 1,* times that of stainless steel, .ts modulus is ((A of steel, The tensile strength ?as an alloy@ of titanium can be comparable to that of lower%strength martensitic stainless and is better than that of austenitic or ferritic stainless steel. including human #ody. itanium is e-ceptionally corrosion resistant, this +eature o+ten e-ceeds that o+ stainless steel in most environments,

2< | P a g e

he commercial alloys o+ titanium are use+ul at temperatures to a#out &/7 GC to &C& GC '(%%% G?to((%% G?), depending on composition. It may #e +orged #y means o+ standard techni0ues.

.t is castable although the in estment casting method is preferred ?in estment casting has a lower cost than the con entional method, The method is ery helpful when intricate shapes are in ol ed@,

.t is joinable ?this may be achie ed by means of fusion bonding, bra8ing, adhesi es, diffusion bonding and fasteners@,

.t is formable and readily machinable,

...,1,- !rystal structure ?2)@:

Titanium has two elemental crystal structures. !ne is #ody centered3 cu#ic structure '@CC), and the other is close pac2ed he-agonal structure 'HC4). he cu#ic structure is +ound only at high temperature and the HC4 he t1o crystal structures o+ titanium structure +ound at lo1 temperature.

are commonly 2no1n as alpha and #eta. Alpha re+ers to he-agonal titanium and #eta re+ers the cu#ic structure. 4ure titanium e-hi#its the allotropic phase trans+ormation at 77$GC changing +rom HC4 'F phase) to @CC 'H phase) and the phases are sho1n in '+ig&). he e-act trans+ormation temperature is strongly in+luenced #y the interstitial and su#stitution elements and also depends upon the purity o+ the metal. he HC4 unit cell o+ H phase is sho1n in '+ig:) indicating room temperature values o+ lattice parameters, aI%.$C&nm and cI%.;:7nm. HC4 structure. he resulting c.a ratio o+ pure alpha titanium is (.&7< and is smaller than the ideal ratio o+ (.:// +or the

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&igure7( Allotropic phase transformation

&igure8( 9nit cells of titanium +0CP and :CC-

...,1,(

+pplications of titanium and its alloys ?2<@

Titanium possesses a uni7ue combination of good mechanical

properties, low density, corrosion resistance and biocompatibility, which make them attracti e candidates for structural and biomedical applications, The two classical application areas are airframes and aero engines which are dri en by the superior structural efficiency of titanium alloys, Due to their high tensile strength to density ratio, high corrosion resistance, high crack resistance, and ability to withstand moderately high temperatures without creeping, titanium is used in aircraft, armor plating, na al ships, spacecraft, and missiles, .n fact, about two thirds of all titanium metal produced is used in aircraft engines and frames, .n the traditional areas of chemical and power industries, usage of titanium alloys as corrosion resistant material has become more common in
*1 | P a g e

recent years ?$chut8 1 =atkins, 1<<)@12, Due to its high corrosion resistance to sea water, titanium is used to make propeller shafts, heat e/changers of desalination plants, heater%chillers for salt water a7uariums and fishing lines, Titanium is used to manufacture the housings and other components of ocean%deployed sur eillance and monitoring de ices for scientific and military use, The former $o iet 5nion de eloped techni7ues for making submarines largely out of titanium, which became both the fastest and deepest di ing submarines of their time, $e eral titanium alloys ha e been used as implant materials, ;fforts ha e been made to de elop new alloys in order to impro e the fatigue strength and biocompatibility ?"roes, +llen, 1 3iinomi, 1<<)@ ?*'@. itanium metal is used in automotive applications, particularly in automo#ile or motorcycle racing, 1here 1eight reduction is critical 1hile maintaining high strength and rigidity. he metal is generally too e-pensive to ma2e it mar2eta#le to the general consumer mar2et, other than high3end products, particularly +or the racing per+ormance mar2et. 8ate model Corvettes have #een availa#le 1ith titanium e-hausts. itanium is used in many sporting goods li2e tennis rac2ets, gol+ items, lacrosse stic2 sha+ts, cric2et, hoc2ey and #icycle +rames and components. Although not a mainstream material +or #icycle production, titanium #i2es have #een used #y race teams and adventure cyclists. he need o+ titanium in consumer itanium is products area is gro1ing very +ast #ecause o+ its dura#ility and preservation o+ the appealing metal sur+ace, particularly +or designer Je1elry. also used +or the surgical instruments used in image3guided surgery, as 1ell as 1heelchairs, crutches, and any other products 1here high strength and lo1 1eight are desira#le'/().

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.B. heory o+ chemisorption and 4hysisorption

.N,1 !hemisorption .N,1,1 #eneral .ntroduction to chemisorption
!hemisorption is a kind of adsorption which in ol es a chemical reaction between the surface and the adsorbate, 3ew chemical bonds are generated at the adsorbant surface, ;/amples include macroscopic phenomena that can be ery ob ious like corrosion and subtler effects

associated with heterogeneous catalysis, The strong interaction between the adsorbate and the substrate surface creates new types of electronic bond ?*2@, In contrast 1ith chemisorption, chemical species leaves the sur+ace 2eeping it intact during 4hysisorption. It is conventionally accepted that the energetic threshold separating the #inding energy o+ K4hysisorptionK +rom that o+ KchemisorptionK is a#out %.& eB per adsor#ed species. Due to speci+icity, '//) the nature o+ chemisorption can greatly di++er, depending on the chemical identity and the sur+ace structure as sho1n in +ig <.

** | P a g e

&igure;( chemisorption of 0) gas on metal surface

.N,1,2 "eatures of !hemisorption

?*-@

The phenomenon is characteri8ed by chemical specificity, !hanges in the electronic state may be detectable by suitable physical means ?e,g, 5,N,, .nfrared or microwa e spectroscopy, electrical conducti ity, magnetic susceptibility@

The chemical nature of the adsorbent?s@ may be altered by surface dissociation or reaction in such a way that on desorption the original species cannot be reco eredB in this sense chemisorptions may not be re ersible,

The energy of chemisorption is of the same order of magnitude as the energy change in a chemical reaction between a solid and a fluidG thus chemisorption, like chemical reactions in general, may be e/othermic or endothermic and the magnitudes of the energy changes may range from ery small to ery large,

The elementary step in chemisorption often in ol es acti ation energy, =here the acti ation energy for adsorption is large ?acti ated adsorption@, true e7uilibrium may be achie ed slowly or in practice not at all, "or e/ample, in the adsorption of gases by solids, the obser ed e/tent of adsorption at a constant gas pressure after a fi/ed time may in certain ranges o+ temperature increase 1ith rise in temperature. In addition, 1here the activation energy +or desorption is large, removal o+ the chemisor#ed species +rom the sur+ace may #e possi#le only

*- | P a g e

under e-treme conditions o+ temperature or high vacuum, or #y some suita#le chemical treatment o+ the sur+ace. 6ince the adsor#ed molecules are lin2ed to the sur+ace #y valence #onds, they 1ill usually occupy certain adsorption sites on the sur+ace and only one layer o+ chemisor#ed molecules is +ormed.

.N,1,* !haracteristics of chemisorption

>igh enthalpyG ('KjFmolPQ>P%)''KjFmol, +dsorption takes place only in a Monolayer, >igh temperature, Type of interactionG strongB co alent bond between adsorbate and surface,

>igh acti ation energy, .ncrease in electron density in the adsorbent%adsorbate inter+ace. Reversi#le only at high temperature. Due to specificity, the nature of chemisorption can greatly differ from system to $ystem depending on the chemical identity and the surface structure

.N,1,-#as%surface !hemisorptions
.N,1,-,1 +dsorption Kinetics
+s an instance of adsorption, chemisorption follows the adsorption process, The first stage is for the adsorbate particle to come into contact with the surface, The particle needs to be trapped onto the surface by not
*( | P a g e

possessing enough energy to lea e the gas%surface potential well, .f it elastically collides with the surface, then it would return to the bulk gas, .f it loses enough momentum through an inelastic collision, then it CsticksD onto the surface, forming a precursor state bonded to the surface by weak forces, similar to Physisorption, The particle diffuses on the surface until it finds a deep chemisorption potential well, Then it reacts with the surface or simply desorbs after attaining enough energy ?*(@. he reaction 1ith the sur+ace is dependent on the chemical species involved. Applying Gi##s +ree energy e0uation +or reactions>

G=H-TS
#eneral thermodynamics states that for spontaneous reactions, the change in free energy should be negati e, $ince a free par ticle is restrained to a sur+ace, and unless the sur+ace atom is highly mo#ile, entropy is lo1ered. his means that the enthalpy term must #e negative, implying an e-othermic reaction I5.'.G.( Mo elin8 "or e/perimental setup o+ chemisorptions, the amount o+ adsorption o+ a particular system is 0uanti+ied #y a stic2ing pro#a#ility value. Ho1ever, chemisorptions are very di++icult to theorize. A multidimensional potential energy sur+ace '456) derived +rom e++ective medium theory is used to descri#e the e++ect o+ the sur+ace on a#sorption, #ut only certain parts o+ it are used depending on 1hat is to #e studied. here e-ist several models to descri#e sur+ace reactions> the 8angmuir3Hinshel1ood mechanism in 1hich #oth reacting species are adsor#ed, and the 5ley3Rideal mechanism in 1hich one is adsor#ed and the other reacts 1ith it. Real systems have many irregularities, ma2ing theoretical calculations more di++icult '/$)

*& | P a g e

$olid surfaces are not necessarily at e7uilibrium, They may be perturbed and irregular. Distri#ution o+ adsorption energies and odd adsorption sites. @onds +ormed #et1een the adsor#ate.

!ompared to Physisorption where adsorbates are simply sitting on the surface, the adsorbates can change the surface, along with its structure, The structure can go through rela/ation, where the first few layers change inter planar distances 1ithout changing the sur+ace structure, or reconstruction 1here the sur+ace structure is changed. I5.'.G.& Dissociation Chemisorption: + particular brand of gas%surface chemisorption is the dissociation of diatomic gas molecules, such as hydrogen, o/ygen, and nitrogen, 4ne model used to describe the process is precursor%mediation, The absorbed molecule is adsorbed onto a surface into a precursor state, The molecule then diffuses across the surface to the chemisorption sites '/:). the molecular #ond in +avor o+ ne1 #onds to the sur+ace. hey #rea2 he energy to

overcome the activation potential o+ dissociation usually comes +rom the translational energy and vi#rational energy. 5-ample is the hydrogen and copper system, one that has #een studied many times over. It has a large activation energy o+ ./& 3 .7& eB. he vi#rational e-citation o+ the hydrogen molecule promotes dissociation on lo1 inde- sur+aces o+ copper ,

.N,2 Physisorption
The fundamental interacting force of Physisorption is caused by an der =aals force, ; en though the interaction energy is ery weak ?R1'E1''
*6 | P a g e

meN@, Physisorption plays an important role in nature. ?or instance, the van der Aaals attraction #et1een sur+aces and +oot3hairs o+ gec2os provides the remar2a#le a#ility to clim# up vertical 1alls. Ban der Aaals +orces originate +rom the interactions #et1een induced, permanent or transient electric dipoles. In comparison 1ith chemisorptions, in 1hich the electronic structure o+ #onding atoms or molecules is changed and covalent or ionic #onds +orm, 4hysisorption, generally spea2ing, can only #e o#served in the environment o+ lo1 temperature 'thermal energy at room temperature L$: meB) and in the a#sence o+ the relatively strong chemisorptions. In practice, the categorization o+ a particular adsorption as 4hysisorption or chemisorptions depends principally on the #inding energy o+ the adsor#ate to the su#strate '/<).

*) | P a g e

&igure<( comparison chemisorptions and Physisorption of gases

.N,2,1 "eature of Physisorption

?*)@

The phenomenon is a general one and occurs in any solidFfluid system, although certain specific molecular interactions may occur, arising from particular geometrical or electronic properties of the adsorbent andFor adsorbate,

; idence for the perturbation of the electronic states of adsorbent and adsorbate is minimal,

The adsorbed species are chemically identical with those in the fluid phase, so that the chemical nature of the fluid is not altered by adsorption and subse7uent desorption,

The energy of interaction between the molecules of adsorbate and the adsorbent is of the same order of magnitude as, but is usually greater than, the energy of condensation of the adsorbate. he elementary step in physical adsorption +rom a gas phase does not involve activation energy. 6lo1, temperature dependent, e0uili#ration may ho1ever result +rom rate3determining transport processes.

.n

physical

adsorption,

e7uilibrium

is

established

between

the

adsorbate and the fluid phase, .n solidFgas systems at not too high pressures, the e-tent o+ physical adsorption increases 1ith increase in
*< | P a g e

gas pressure and usually decreases 1ith increasing temperature. In the case o+ systems sho1ing hysteresis the e0uili#rium may #e metasta#le. "nder appropriate conditions o+ pressure and temperature, molecules +rom the gas phase can #e adsor#ed in e-cess o+ those in direct contact 1ith the sur+ace.

N,;9P;0.M;3T+2 T;!>3.S5;$ N,1, .3T04D5!T.43 T4 TPD04

?&H, G%7

.
Re uction;

*Bi ation7

6.emperature

Pro8ramme

Desorption;

The characteri:ation of solids, intended as knowledge of chemical-ph ysical properties,

structure, surface activity etc, is e9tremely important, particularly in the field of catalytic systems.

The major application of the surface acti ity is related to the catalysis field.
The metal supported catalysts are used in most manufacturing processes of different industries, from the petrochemical field to fine chemistry, from the pharmaceutical field to the food industry. In general they are capable of optimi:ing the yield of a reaction by increasing its kinetics or allowing the use of less drastic conditions for its occurrence and thus reducing the manufacturing cost. -' | P a g e

&igure=( $PDR5 ''>> $hermo model system.

The solid catalysts act by providing specific sites for the adsorption of molecules reacting on the surface, loosening their links and making the reaction easier. In some instances they can react selectively by inhibiting the reaction towards undesired products. @nce the reaction is over, desorption of products from the catalyst surface makes the sites available for another reaction. In most cases, the activity of a supported catalyst is proportional to the metal area, and the activity of this area is a function of the si:e of the metal particles deposited on the inert support. To quantitatively assess the metal surface accessible to the adsorbed molecules, a few analytical methods are available and the use of which depends on the nature of the application of the catalyst under test.

Two analytical methods for the chemisorption of gases are available to calculate the metal surface area of
a catalystA

T The static volumetric method T The in-flow methods applied with the TBD$@.

N.'.'.

Principles an
)

Metho s

The analytical methods available with the TBDC$C@ ..44 allow the determination of the gas quantity '! , @ , 6@, etc.1 chemically adsorbed from the surface of a solid sample with the choice of
)

-1 | P a g e

appropriate e9perimental conditions 'temperatures, pretreatments, etc.1. They also allow the determination of the type and number of the active sites, the evaluation of different thermodynamic and kinetic parameters and the quantitative assessment of the reactivity of the systems towards all gases. inally it is possible to perform very precise quantitative measurements of the acid and basic properties of the systems under test.

N.'.(. In#,lo< Metho

This analytical method adopts conditions of atmospheric pressure, using gas flows 'inert or reactive1.The in-flow systems provide the advantage of being rapid and sensitive, and they do not need calibrations concerning instrumental dead volumes and also reduce the problem of weakly adsorbed gas. " qualitative description of the tests available with the in-flow instrument TBDC$C@ ..44 is reported hereunder.

N.'.&. .PD 6.emperature Pro8ramme Desorption7

The TBD analysis allows defining the strength, the number and the type of active sites available on the surface of a catalyst by the determination of the quantity of gas desorbed from the catalyst submitted to a linear temperature ramp. "fter degassing, reducing or otherwise pretreating the sample to be analy:ed in order to eliminate contaminants, such as water naturally adsorbed on the sample surface, a constant flow of properly chosen reactive gas is conveyed onto the sample to allow the reaction between the sample active sites and the reactive gas according to a known stoichiometry.

4nce the chemisorptions of the reactive gas is over, desorption is performed by linearly
increasing the sample temperature. The catalyst is placed into a reactor crossed by a flow of inert gas 'nitrogen, helium, argon1, which acts as carrier gas for the molecules of reactive gas desorbing from the sample.

=hen the temperature at which heat e/ceeds the energy of acti ation of the gas%solid system is reached, the link between the atoms of adsorbate and adsorbent is broken, and the phenomenon of programmed thermal desorption takes place,
The desorbed molecules are dragged by the carrier gas as far as a thermal conductivity detector 'T6D1, which measures the difference of concentration of the desorbed gas versus a reference flow. =here necessary, a mass spectrometer can also be connected for a precise assessment of the nature of the desorbed species.

-2 | P a g e

The volume of the desorbed species, which can be calculated by appropriate calibrations of the instrument, together with the knowledge of the stoichiometric factor of the chemical reaction and the desorption temperature, allow to calculate the number and the strength of the active site.

N.'.G. .PR 6.emperature Pro8ramme Re uction7

The TB$ analysis allows determination of the number and quantity of the reducible species present in the sample and the temperature at which the reduction itself takes place as a function of the flow conditions, the percentage of reactive gas, the quantity of sample and the speed of the temperature increase. The gas used for this type of analysis is a mi9ture of reactive gas with an inert gas, as hydrogen in argon or nitrogen at 3 or .4D. #enerally the sample is previously o9idi:ed or pretreated to eliminate possible contaminants and completely o9idi:e the metal portion of the catalyst. "lso for this type of analysis, the sample is submitted to a linear increase of temperature and to a constant flow of the gas mi9ture. The reaction generally starts at room temperature, but at an e9tremely low rate, therefore negligible. "t a certain temperature, the reaction rate becomes considerable and the hydrogen consumption can be monitored through the T6D detector. The signal integration allows calculation of the quantity of hydrogen consumed and therefore the number of reacting sites. The TB$ analysis also allows checking the presence of different states of o9idation of the contained metals.

N.'.I. .P* 6.emperature Pro8ramme *Bi ation7

The TB@ analysis allows evaluation of the temperature range in which a sample undergoes o9idation due to an o9idi:ing agent contained in a gas mi9ture such as @ )C!e 3D that is flown inside the reactor containing the sample. In this case, too, the sample is pretreated and the metal o9ides are previously reduced with pure hydrogen before they are submitted to the gas mi9ture flow and to the linear temperature ramp to record the o9ygen consumption.

N.'.$. .emperature Pro8ramme Reaction

Eesides mi9tures of hydrogen and o9ygen in inert gases, the use of other reactive gases of acidic or basic type is possible for the assessment of the basic and acidic sites present in a solid. In

general, the analyses in programmed temperature ramp provide spectra where the temperature is put in relation to the intensity of the signal, which on its turn is proportional to the adsorbed or
-* | P a g e

desorbed gas. The e9act amount of gas involved in the process is determined by means of appropriate calibrations.

N.'.9. Pulse Chemisorption

This type of analysis is performed under isothermal condition. " suitable sampling
system injects known constant amounts of reactive gas 'e.g., hydrogen or o9ygen1 and they come in contact with the sample surface sites accessible to the gas molecules. The active surface coming in contact with the reactive gas chemisorbs a certain quantity there-of, until complete saturation of the sites. The total amount of chemisorbed gas is calculated by difference between the area of the peaks recorded at the end analysis 'saturated sample1 and the areas of the peaks recorded at the beginning of the analysis 'when the chemisorption occurs and the sample is not yet saturated1. It has to be stressed that this type of analysis is e9tremely quick and reproducible.

N.'.J.

Pretreatment o! Samples

Eefore being submitted to any of the described analyses, the samples must be properly pretreated to obtain easily interpretable results.

The sample used must generally ha e a weight ranging from ',''( g to 1g, according to the characteristics of the sample itself, .t usually consists of powders, pellets or balls of solid material containing a certain percentage of metal or Cacti eD phase deposited on an inert support ?e,g,, alumina, silica, etc,@, The pretreatment is performed to remo e contaminants ?e,g,, carbon compounds@ or adsorbed gases that may contribute to errors in the analytical results, as
for instance water. These substances are generally removed by submitting the sample to a gas flow 'reactive or inert1 and to a temperature increase leading to desorption and removal of the undesired substances.

N.'.H

"pplications
The samples that can be characteri:ed belong to the following applicative fieldsA -- | P a g e

T>eterogeneous catalysis, TMetal corrosion, TMeasurement of the acidity and basicity of surfaces, T0educibility ?o/idability@ of materials, The instrument used for measuring the !hemisorption surface area is TPD04 Thermo Modal 11'' and is shown in the following fig <,

N,2, .3T04D5!T.43 T4 90D

N,2,1, :rief >istory and de elopment of 90D
9%ray photon is a form of electromagnetic radiation production following the ejection of an orbital electron and subse7uent transition of atomic orbital electron from states to high to low ener gy. Ahen he monochromatic #eam o+ MNray photons +all onto a specimen, three #asic phenomena may result, namely a#sorption, scatter 'or) +luorescence. the generation o+ di++raction ma-ima. scattered photons may undergo su#se0uent inter+erance leading in turn to hese three #asic phenomena +orm the #ases o+ three important -3ray methods, the a#sorption techni0ue, 1hich is the #asis o+ radiographic analysis, the scattering e++ect, 1hich is the #asis o+ MR? 6pectrometry and M3ray di++ratction studies +or determining lattice parameters. The /%ray was disco ered by =ilhelm 0oentgen in 1)<( a professor of physics at the 5ni ersity of "reiberg, #ermany, accidentally disco ered C9%radiationD, 0oentgen was unsuccessful in his efforts to measure the wa elength of 9%rays but he was successful in showing that 9%rays penetrate matter, including human flesh and show density contrasts, >e recorded the /%ray image of his wife*s hand, +or e-ample as seen #elo1 in +ig (%. He 1as a1arded the +irst No#el 4rize in 4hysics in (C%( +or his discovery o+ this mysterious ne1 +orm o+ highly penetrating radiation ';().
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&igure'>( A Simple 3?ray image

.n 1<12 Ma/ on 2aue, a professor of physics at the 5ni ersity of Munich in #ermany, suggested to one of his research assistants ?=alter "riedrich@ and a doctoral student ?Paul Knipping@ that they use 9%rays in the first diffraction e/periment, The crystal used for this pioneering e/periment was copper sulfate, Non 2aueUs reasoning was that ?#rays have a istances in crystals, an as a act as a &#D i!!raction 8ratin8 , >e was able <avelen8th similar to the interatomic result, the crystal shoul

to demonstrate in a later e/periment on sphalerite ?Vn$@ that the pattern recorded by "riedrich and Knipping for copper sulfate on photographic film was due to diffraction of the Vn$ crystal, ery short wa elength electromagnetic radiation ?about 1,( W, where 1W K 1' %) cm@ from a regular arrangement of atoms in .f the interatomic distances in the crystal are known ?as they were in cubic Vn$@, then the wa elength of the 9%rays can be measured, or alternati ely, if the wa elength is known, diffraction e/periments can be used to determine the interplanar spacingUs of a crystal, Non 2aue, as well as "riedrich and Knipping were awarded 3obel Pri8es in Physics for their disco eries in ol ing 9%ray diffraction, In (C(/ Ailliam H. @ragg and his son Ailliam 8. @ragg '"niversity o+ Manchester, 5ngland) determined the +irst mineral structure 'NaCl) +rom MRD, and also determined the atomic3level structure o+ many more minerals including those o+ pyrite '?e6 $), +luorite 'Ca?$), and calcite 'CaC!/). hey also simpli+ied von 8aue*s mathematical generalization and
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introduced the no1 +amous @ragg e0uation +n@ A )d SinB), 1hich descri#es the condition +or di++raction to occur in terms o+ the 1avelength o+ the M3ray radiation 'O), the interplanar 'PdQ) spacing*s o+ the crystal, and the angle o+ incidence o+ the radiation 1ith respect to the crystal planes 'R). ?ather and son @ragg shared the No#el 4rize in 4hysics +or their contri#utions to this ne1 +ield, 1hich #ecame 2no1n as -3ray crystallography ';$).

N,2,2, The ;lectromagnetic $pectrum, generation of 9% rays, and the :raggsU ;7uation
Nature o+ M3rays> M3rays can #e thought o+ as 1aves 1ith 1avelengths on the order o+ %.( S to (% S. 6horter the 1avelength, the more energetic the 1ave. @ecause o+ the relatively short 1avelengths o+ electromagnetic radiation in the M3ray region, M3rays are high energy 1aves and are much more penetrating compared to "B, visi#le, IR, or radio 1aves. he conversion #et1een energy, +re0uency, and 1avelength is the 1ell3 2no1n de@roglie relationship> C A hD A hcE@, 1here D is the +re0uency, h is 4lanc2*s constant ':.:$ - (%3/; T.s), c is the speed o+ light '$.CC7 (%7m.sec), and @ is the 1avelength o+ the radiation ';/).

N,2,*, #eneration of 9 rays

=hen electrons strike a metal anode with sufficient energy, 9%rays are produced, This process is typically accomplished using a sealed /%ray tube, which consists of a metal target ?often copper metal@ and a tungsten metal filament, which can be heated by passing a current through it ?typically 1'%1( m+@, resulting in the Cboiling offD of electrons from the hot tungsten metal surface, These ChotD electrons are accelerated from the
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tungsten filament ?negati e bias@ to the metal target ?positi e bias@ by an applied oltage ?typically 1(%*' kilo olts@, The collision between these energetic electrons and electrons in the target atoms results in electron from target atoms being e/cited out of their core%le el orbitals, placing the atom in a short%li ed e/cited state, The atom returns to its ground state by ha ing electrons from lower binding energy le els ?i,e, le els further from the nucleus@ making transitions to the empty core le els,

&igure''( characteristic emission spectra of the target material

he di++erence in energy #et1een these lo1er and higher #inding energy levels is radiated in the +orm o+ M3rays. his process results in the production o+ characteristic M3rays in +ig ($ 'i.e. M3 rays 1hose energies are uni0ue to the target metal due to the 0uantized nature o+ the electron energy levels o+ each atom and the uni0ue energies o+ these energy levels) UCu =H('8/ to = electronic transition> 5 I 7%;<.<7 eB, O I (.&;%&( S), Cu =H$'8$ to = electronic transition> 5 I 7%$<.7/ eB, O I (.&;;// S), Cu =F('M/ to = electronic transition> 5 I 7C%&.$C eB, O I (./C$(< S)V. hus M3rays provide a convenient means o+ determining 1hat elements are present in a sample #ecause o+ the uni0ue 1avelengths produced #y each uni0ue element. A lo1er energy
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process that involves the interaction o+ electrons 1ith the nucleus o+ an atom in the target metal produces a continuum o+ lo1er intensity M3 radiation over a #road energy range 2no1n as @remstrahllung ';;). As the voltage on an M3ray tu#e is increased, the characteristic line spectra o+ the target element are superimposed upon the continuous spectrum 'at right).

&igure')( "eneration of 3?rays

N,2,-, 9%ray diffraction

Crystals are ordered 1ith three3dimensional arrangements o+ atoms 1ith characteristic periodicities. As the spacing #et1een atoms is on the same order as M3ray 1avelengths '(3/ S), crystals can di++ract the radiation 1hen the di++racted #eams are in3phase. given as n@ A )dsinB. occur at a certain angle 'R) +or a given d3spacing. he @ragg e0uation is ?or a given 1avelength 'O), di++raction can only

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.t should be taken into account that if only two planes of atoms were diffracting, as sho1n in the +ig(/, then the transition to +rom constructive destructive

inter+erence 1ould #e gradual as the angle is varied. Ho1ever, since many atomic planes are inter+ering in real materials, very sharp pea2s surrounded #y
&igure'.( 3 ray Diffraction

mostly destructive inter+erence result ';;)

N,2,(, $ingle !rystal ?2aue@ Diffraction

2aue Diffraction is one of the oldest, common 9%ray techni7ues, + single crystal of the material is irradiated with a beam of 9%rays, The diffracted beams produce spots on photographic film, + series of diffraction spots surround the central '+ig(;).
&igure'/( laue diffraction pattern

point

o+

the

#eam,

corresponding

to

di++raction +rom a given series o+ atomic planes

he position o+ the #eam depends on the @ragg di++raction angle, 1hich is determined #y the 1avelength o+ the M3rays and the periodic spacing o+ the crystal planes o+ atoms 'interplanar spacing ';&). The symmetry of the diffraction pattern shows the symmetry of the crystal, 9%rays are used to study the crystal structure of materials, "or e/ample, the 9%ray diffraction spectra can be used to identify a material,

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&igure'7( Modern Automated 3?ray Diffractometer

N,2,&, Powder Diffraction

+ powder is used to ensure completely random crystal orientation to get diffraction from all possible planes, The diffraction pattern can be recorded on a flat photographic film or on a !0T ?cathode ray tube@, =hen the incident beam satisfies the :ragg condition, a set of planes forms a cone of diffracted radiation at an angle to the sample, $ince the cone of 9%rays intersects the flat photographic filmstrip in two arcs e7ually spaced from the direct 9%ray beam, two cur ed lines will be recorded on the photographic film, The distance of the lines from the center can be used to determine the angle, which can then be used to determine the inter% planarXdU spacing ?-&@, M3ray po1der di++ractometers record all re+lections using a scintillation detector 'in counts per second o+ M3rays). he pattern o+ di++racted M3rays is uni0ue +or a particular structure type and can #e used as a P+ingerprintQ to identi+y the structure type. Di++erent minerals have di++erent structure types, thus M3ray di++raction is an ideal tool +or identi+ying di++erent minerals.

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&igure'8( $*o 3?ray diffraction patterns produced on photographic film using the De#ye?Scherrer po*der cameras on the 3?ray diffraction generator.

&igure';( 3?ray diffraction pattern for a po*der sample + aCl-

The diffraction pattern of an unknown sample is measured and is compared with already known standards ?Y!PD$ cards@ to identify it, .he po< er i!!racto8ram o! a compoun is its K!in8erprintL an can =e use to i enti!y the compoun
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N,2,6, $cherrer e7uation

The $cherrer method predicts the si8e of crystallites, instead of the si8e of particle, 2arge particles might contain se eral crystallites, >owe er, it is common that nanometer%si8ed particle contains only one crystallite, Therefore, the si8e of crystallites in nanometer%si8ed Particle as predicted by the $cherrer relation also indirectly figures out the si8e of particle itself, ;/periments pro ed that the smaller the crystallite si8e, broader the diffraction peak, Nery large crystal with a single orientation produces diffraction peaks which are nearly ertical line in shape, 4n the other hand, small crystal produces ery wide peak, Therefore, the width of the diffraction peaks gi es information on the crystal si8es ?-(@,

.hickness, t O %.H M; 6) cos N)7

t K thickness of crystallite M K /%ray wa elength ) K "=>M ?full width at half ma/@ or integral breadth N) K :ragg +ngle

N,2,), +pplication ?-6@

6dentificationG The most common use o+ po1der 'polycrystalline) di++raction is chemical analysis. his can include phase identi+ication 'search.match),
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investigation

o+

high.lo1

emperature

phases,

solid

solutions

and

determinations o+ unit cell parameters o+ ne1 materials. Polymer crystalline( + polymer can be considered partly crystalline and partly amorphous, The crystalline domains act as a reinforcing grid, like the iron framework in concrete, and impro e the performance o er a wide range o+ temperature. Ho1ever, too much crystalinity causes #rittleness. component gives a very #road pea2 'halo). he crystalline parts give sharp narro1 di++raction pea2s and the amorphous he ratio #et1een these Intensities can #e used to calculate the amount o+ crystalline in the material.

N,*, $!+33.3# ;2;!T043 M.!04$!4PZ ?$;M@ N,*,1, =hat is $canning ;lectron Microscopy ?$;M@
The scanning electron microscope ?$;M@ uses a focused beam of high%energy electrons to generate a ariety of signals at the surface of solid specimens, The signals that deri e from electron% sample interactions re eal information about the sample including e/ternal morphology ?te/t ure), chemical composition, crystalline structure and orientation o+ materials ma2ing up the sample. In most applications, data are collected over a selected area o+ the sur+ace o+ the sample, and a $3dimensional image is generated that displays spatial variations in these properties. Areas ranging +rom appro-imately ( cm to & microns in 1idth can #e imaged in a scanning mode using conventional 65M techni0ues 'magni+ication ranging +rom $%M to appro-imately /%,%%%M, spatial resolution o+ &% to (%% nm). he 65M is also capa#le o+ per+orming analyses o+ selected point locations on the sample,
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this approach is especially use+ul in 0ualitatively or semi30uantitatively determining chemical compositions 'using 5D6), crystalline structure, and crystal orientations 'using 5@6D). he design and +unction o+ the 65M is very similar to the 54MA and considera#le overlap in capa#ilities e-ists #et1een the t1o instruments ';7).

N,*,2 "undamental Principles of $canning ;lectron Microscopy ?$;M@

Accelerated electrons in an 65M carry signi+icant amounts o+ 2inetic energy and this energy is dissipated as a variety o+ signals produced #y electron3sample interaction 1hen the incident electrons are decelerated in the solid sample. hese signals include secondary electrons 'that produce 65M images), #ac2scattered electrons '@65), di++racted #ac2scattered electrons '5@6D that are used to determine crystal structures and orientations o+ minerals), photons 'characteristic M3rays that are used +or elemental analysis and continuum and heat. M3rays), 6econdary visi#le electrons light and 'cathodoluminescence33C8),

#ac2scattered electrons are commonly used +or imaging samples> secondary electrons are most valua#le +or sho1ing morphology and topography on samples and #ac2scattered electrons are most valua#le +or illustrating contrasts in composition in multiphase samples 'i.e. +or rapid phase discrimination). M3ray generation is produced #y inelastic collisions o+ the incident electrons 1ith electrons in discrete or#ital 'shells) o+ atoms in the sample. As the e-cited electrons return to lo1er energy states, they yield M3 rays that are o+ a +i-ed 1avelength 'that is related to the di++erence in energy levels o+ electrons in di++erent shells +or a given element) ';:). hus, characteristic M3rays are produced +or each element in a mineral that is Ke-citedK #y the electron #eam. 65M analysis is considered to #e Knon3 destructiveK, that is, -3rays generated #y electron interactions do not lead to volume loss o+ the sample, so it is possi#le to analyze the same materials repeatedly.
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N,*,* $canning ;lectron Microscopy ?$;M@ .nstrumentation % >ow Does .t =ork[

&igure'<( Diagram of Scanning Clectron Microscopy +SCM-

;ssential components of all $;Ms include the followingG

;lectron $ource ?\#un\@ ;lectron 2enses $ample $tage Detectors for all signals of interest Display F Data output de ices .nfrastructure 0e7uirementsG

Power $upply Nacuum $ystem !ooling system

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Nibration%free floor 0oom free of ambient magnetic and electric fields

65Ms al1ays have at least one detector 'usually a secondary electron detector), and most have additional detectors. he speci+ic capa#ilities o+ a particular instrument are critically dependent on 1hich detectors it accommodates. The $;M is an instrument that produces a largely magnified image by using electrons instead of light to form an image, + beam of electrons is produced at the top of the microscope by an electron gun, The electron beam follows a ertical path through the microscope, which is held within a acuum, The beam tra els through electromagnetic fields and lenses, which focus the beam down toward the sample ?-<@, 4nce the beam hits the sample, electrons and 9%rays are ejected from the sample, Detectors collect these 9%rays, backscattered electrons, and secondary electrons and con ert them into a signal that is sent to a screen similar to a tele ision screen, This produces the final image,

N,*,-, >ow is a sample prepared

:ecause the $;M utili8es acuum conditions and uses electrons to form an image, special preparations must be done to the sample, +ll water
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must be remo ed from the samples because the water would apori8e in the acuum, +ll metals are conducti e and re7uire no preparation before being used, +ll non%metals need to be made conducti e by co ering the sample with a thin layer of conducti e material, This is done by using a de ice called a \sputter coater,\

N,*,( $trengths and 2imitations of $canning ;lectron Microscopy ?$;M@[ ?('@ ...,*,(,1 $trengths
here is argua#ly no other instrument 1ith the #readth o+ applications in the study o+ solid materials that compares 1ith the 65M. he 65M is critical in all +ields that re0uire characterization o+ solid materials. Ahile this contri#ution is most concerned 1ith geological applications, it is important to note that these applications are a very small su#set o+ the scienti+ic and industrial applications that e-ist +or this instrumentation. Most 65MEs are comparatively easy to operate, 1ith user3+riendly KintuitiveK inter+aces. Many applications re0uire minimal sample preparation. ?or many applications, data ac0uisition is rapid 'less than & minutes.image +or 65I, @65, spot 5D6 analyses.) Modern 65Ms generate data in digital +ormats, 1hich are highly porta#le.

...,*,(,2 2imitations
6amples must #e solid and they must +it into the microscope cham#er. Ma-imum size in horizontal dimensions is usually on the order o+ (% cm, vertical dimensions are generally much more limited and rarely e-ceed ;% mm. ?or most instruments samples must #e sta#le in a vacuum on the order o+ (%3& 3 (%3: torr. 6amples li2ely to outgas at lo1 pressures 'roc2s saturated 1ith hydrocar#ons, K1etK samples such as coal, organic materials or s1elling clays, and samples li2ely to decrepitate at lo1 pressure) are unsuita#le +or e-amination in conventional 65MEs. Ho1ever,
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Klo1 vacuumK and KenvironmentalK 65Ms also e-ist, and many o+ these types o+ samples can #e success+ully e-amined in these specialized instruments. 5D6 detectors on 65MEs cannot detect very light elements 'H, He, and 8i), and many instruments cannot detect elements 1ith atomic num#ers less than (( 'Na). Most 65Ms use a solid state M3ray detector '5D6), and 1hile these detectors are very +ast and easy to utilize, they have relatively poor energy resolution and sensitivity to elements present in lo1 a#undances 1hen compared to 1avelength dispersive M3ray detectors 'AD6) on most electron pro#e micro analyzers '54MA). An electrically conductive coating must #e applied to electrically insulating samples +or study in conventional 65MEs, unless the instrument is capa#le o+ operation in a lo1 vacuum mode.

N,-, :;T ?:runauer, ;mmett and Teller@%$urface area Determination N,-,1, .ntroduction
The surface of a material is the di iding line between a solid and its surroundings, namely li7uid, gas or another solid, =e can anticipate therefore, that the amount of surface, or surface area, is an important factor in the beha ior of a solid, $urface area affects, for e/ample, dissolution rates of pharmaceuticals, the acti ity of an industrial catalyst, how fast cement hydrates, adsorption capacity of air and water purifiers, and the processing of most powders and porous materials, =hene er solid matter is di ided into smaller particles new surfaces are created thereby increasing the surface area, $imilarly, when pores are created within the particle interior ?by dissolution, decomposition or some other physical or chemical means@ the surface area is also increased ?(1@,

N,-,2, +ssumptions of :;T ;7uation

The :;T .sotherm ?named for its in entors, :runauer, ;mmett, and Teller@ allows nitrogen molecules to adsorb on each site, The assumptions used to deri e the :;T isotherm are
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1, #aseous molecules beha e ideally 2, Multiple nitrogen molecules can be adsorbed to each site *, ;ach adsorbed molecule pro ides a site for the adsorption of the molecule in the layer abo e it -, +ll sites on the surface are e7ui alent (, 3o adsorbate % adsorbate interactions &, +n adsorbed molecule is immobile 6, 3itrogen in the second and higher layers is assumed to be li7uid like,

N,1,*, #as $orption

The true surface area, including surface irregularities and pore interiors, cannot be calculated from particle si8e information, but is rather determined at the atomic le el by the adsorption o+ nonreactive, or inert gas, The amount adsorbed, letUs call it M, is a function not only of the total amount of e/posed surface, but also ?i@ temperature, ?ii@ gas pressure and ?iii@ the strength of interaction between gas and solid, $ince most gases and solids interact weakly, the surface must be cooled substantially in order to cause measurable amounts of adsorption E enough to co er the entire surface, +s the gas pressure is increased, more gas molecules gets adsorbed on the surface ?in a non%linear way@, :ut, adsorption of a cold gas does not stop when it has co ered the surface in a complete layer one molecule thick ?letUs call the theoretical monolayer amount of gas 5m@] +s the relati e pressure is increased, e/cess gas is adsorbed to form PmultilayersQ. $o, gas adsorption % as a function of pressure % does not follow a simple relationship, and we must use an appropriate mathematical model to calculate the surface area, =e use the :;T e7uation ?(2@

';5 P6Po; P7#'Q O 6C#'7 6Po; P7 ; 5m C F'; 5m C

=here
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N% Nolume of gas adsorbed, P% ;7uilibrium pressure of adsorbent, Po% saturation apour pressure, Nm% monolayer olume of adsorbant, !%:;T constant

N,-,-, .sotherm types

?(*@

&igure'=( types of isotherm

$ype 6
Pores are typically microspores with the e/posed surface residing almost e/clusi ely inside the microspores, which once filled with adsorbateB lea e little or no e/ternal surface for further adsorption

$ype 66

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Most fre7uently found when adsorption occurs on nonporous powders or powders with diameters e/ceeding microspores, .nflection point occurs near the completion of the first adsorbed monolayer

$ype 666
.sotherm characteri8ed by heat of adsorption lesser than the heat of li7uefaction of adsorbate, +dsorption proceeds as the adsorbate interaction with an adsorbed layer is greater than the interaction with the adsorbent surface

$ype 6V
4ccur on porous adsorbents with pores in the range of 1,( E 1''nm, +t higher pressures the slope shows increased uptake of adsorbate as pores become filled, inflection point typically occurs near completion of the first monolayer

$ype V
+re obser ed where there is small adsorbate absorbent interaction potentials ?similar to type ...@, and are also associated with pores in the 1,( E1''nm range,

N,-,(, Principles of Measurement

The gas most commonly used is nitrogen, "irstly, it is readily a ailable in high purity, $econdly, the most appropriate coolant, li7uid nitrogen, is also readily a ailable, Thirdly, the interaction of nitrogen with most solid surfaces is relati ely strong, 2astly, there is wide acceptance of the cross3sectional area, .n the classical manometric techni7ue, relati e pressures less than unity are achie ed by creating conditions of partial acuum ?absolute pressures of pure nitrogen below atmospheric pressure@, >igh%precision and accurate pressure transducers monitor those pressure
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changes ?in a fi/ed and known

olume@ due to the adsorption process . This

method is easily automated and the amount of gas adsorbed is made at a number different relati e pressures, 5sually, the analy8er obtains at least three data points in the relati e pressure range between ','2( torr and ',*' torr, ;/perimentally measured data are recorded as pairs of aluesG the amount of gas adsorbed ?Bads@ and the corresponding relati e pressure ?4.4o@, + plot of these data is called an isotherm, The :;T analyser used in the present study is shown in "ig2',

&igure)>( :C$? sorptomotic?'==>

N,-,&, Principles of !alculation

The computer program takes o er and a least%s7uares linear regression is used to fit the best straight line through a trans+ormed data set consisting of the following pairs of aluesG

';P5a s6P%;P7#'Q and P;Po, The monolayer capacity, 5m, is calculated

from the slope, S, and the intercept, i, of the straight line,
SA+C?'-EVmC &* | P a g e

iA'EVmC

$ol ing for 5m,

5mO';6sFi7
3ow we need the number of molecules in the monolayer, and we get from that the number of moles, Yust di ide 5m by the molar olume ?M5) for the number of moles, Multiply number of moles by + ogadroUs number to arri e at the number of molecules co ering the surface in a layer one molecule thick, .f we know how much area one molecule occupies, the total area is one simple multiplication of number of molecules with cross sectional area of a molecule, Different gas molecules ha e different si8es and occupy different areas, =e call that area the Ccross3sectional areaD?(*@ , Therefore, the total surface area, St, is then calculated from

StO5mR:"vR"m;M5

=here :"v is + ogadroUs number, "m is the cross%sectional area, M5# molar olume of the sample and 5m%3umber of moles, ?The surface area community@ takes a pragmatic approach, and assumes it to be 1&,2 s7uare angstroms ?',1&2 nm2@ on all surfaces, +ll surface area results are finally reported normali8ed by sample weight, or mass, as s7uare meter per gram, written m2Fg or m2g%1,

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N.,;9P;0.M;3T+2 N.,1 !haracteri8ation of !hemisorption ?TPD04@G

TPD04 e7uipment ?Thermo Modal 11''@ was used for the characteri8ation of chemisorption surface area of the hydrogen storage material, namely Ti and is shown in the figure ?1*@, TPD04 11'' is the single instrument in which one can do temperature programmed desorption ?TPD@, reduction ?TP0@ and o/idation ?TP4@ and pulse !hemisorption using a range of pure gas and mi/tures, .t can perform the acti ation of one material in one reactor while analy8ing another on the same instrument, The instrument comes as standard with two electrically heated o ens, TPD04 11'' is an automatic surface area characteri8ation unit with good sensiti ity, This instrument was used for the characteri8ation of titanium powder by purging the probe gas such as hydrogen carried by carrier gas such as argon to the reactor, The chemisorption of hydrogen by the titanium sample was carried out by temperature programmed reduction ?TP0@ and temperature programmed desorption ?TPD@, During the TP0 process, some of the supplyied hydrogen gets chemisorbed on the sample used for analysis ?Ti@ and the remaining gas will pass into the T!D producing the signal, Thus
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the chemisorption of hydrogen is monitored online by logging the T!D signal, The 7uantity of >2 chemisorbed is obtained by the integration of TP0 and TPD cur es, Prior to the analysis, the T!D signal was calibrated by injection of known mass of hydrogen, The reactor essel used in the e/periements is made up of twin 7uart8 tubes in inner and outer configuration, $ample gas enters through outer tube and then enters into the inner tube through bottom hole and passes o er sample and then reaches the T!D detector,

&igure )'( Schematic representation of Pulse Chemisorption in $PDR5

:efore doing the e/periment, the reactor essels were washed with soap solution and dried in acuum o en for an hour to remo e any contamination of the sample, Pure titanium powder was placed between glass wool in the inner tube of reactor, Then the reactor was fitted into the instrument, The sample was pretreated by flushing with 5>P argon at room temperature for some time and then heated to 12( '! to remo e any olatile materials and moisture present in the sample, +fter completing the pretreatment, the sample was processed for analysis mode, TP0 and TPD
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analysis for the >2 chemisorption was carried out as function of temperature from -''o! to &''o!, >eating rates is 2'o!Fmin to optimi8e the heating parameters at which net hydrogen uptake efficiency was ma/imum, .n TP0 in analysis mode, hydrogen gas from hydrogen generator was purged at constant flow rate through the reactor using argon carrier gas and sample was heated to pre%determined temperature at the fi/ed heating rate,

+fter the TP0, the samples were subjected to TPD analysis at the same fi/ed temperature to estimate the release of hydrogen at the corresponding temperature, "rom the TP0 and TPD profile, the net hydrogen chemisorption at the particular temperature was determined, The TP0 and TPD analysis were carried out as a function of heating rate to study the mechanism of titanium hydrogen reaction and to calculate the acti ation energy of the reaction,

N.,2 characteri8ation using 90D Techni7ueG

9%ray powder diffraction ?90D@ is a rapid nondestructi e analytical techni7ue primarily used for phase identification of a crystalline material and can pro ide information on unit cell dimensions and to determine the particle si8e, 90D studies were carried out for the Different Titanium samples collected from arious sources as gi en below ?i@Pure Ti Powder?+lpha +ldrich@ ?ii@!ommercial Titanium hydride?+lpha +ldrich@ ?iii@Titanium Powder $ubjected to full cycles of TPD04
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The typical instrument related parameters were operating

oltage of -' kN,

current of *' m+ for the /%ray tubeB scan speed of ','2$ %1 with counting time of *s per step and an angular range ?2@ of 1' ' to )'', The 9%ray diffractometer was calibrated using silicon $0M &-'a as an e/ternal standard, $cintillation detector was used to detect the diffracted 9%rays, The sample was installed in 8ero reflection glass plate and mounted on to the sample holder of the 9%ray powder diffractometer, + collimated beam of the 9%rays was allowed to fall onto the sample, The diffracted 9%rays were made to fall on the detector by mo ing the detector by an angle of 2 ^ degrees relati e to the incident beam, The detector output was collected and stored in a data base, The relati e intensities were plotted as a function of 2 ^ to obtain the diffractogram and were superimposed in order to facilitate inter%comparison,

N.,* !haracteri8ation of Physisorption surface area using ?:;T@,

#as adsorption was the most widely used techni7ue for the total surface area measurements, #as molecules of known si8e are condensed onto the unknown sample surface, by completely co ering the surface and opening the pores of each particle with a condensed gas, The gas surface area analy8er can be characteri8ing the surface, including irregularities and the pore interiors down to an atomic le el, The techni7ue re7uires a clean surface, as the sample has to be taken to an ele ated temperature under acuum to CoutgasD as a necessary step, To measure the Physisorption surface area of the titanium sample, Cout gassingD is the first step to remo e any impurities and moisture present in the surface of the sample, "or out gassing 1g of sample was taken in the sample holder and subjected to out gassing at 12( _! for 2- hrs, +fter out gassing the sample is

&) | P a g e

ready for analysis, The instrument is used for the measurement of Physisorption surface area, 3itrogen is often the gas used as its molecular si8e was inert and was a ailable in high purity at a reasonable cost, The Cout gassedD sample under high acuum in the sample tube is immersed in a coolant bath of li7uid nitrogen at %1<(_!, +t this stage the sample is ready to attract gas molecules onto it when they are admitted to the sample tube, + layer of inert gas will physically adhere to the sample surface, lowering the pressure in the analysis chamber, .,e, the initial pressure is kept to be 1''' torr while adsorption takes place it becomes some <6', <)'torr at regular inter als, 4nce all the molecules get adsorbed on the surface it is maintained at the same pressure, +fter completion of adsorption the Dewar flask containing li7uid 3itrogen was withdrawn and temperature rose to some le el, it gi es desorption of 3itrogen gas, The signal was monitored by T!D,

The olume of 3itrogen desorbed from the sample is related with the pressure of the system, "rom the measured absorption isotherm of the e/periment, the surface area of the sample can be calculated, Therefore a higher surface area material is more likely to react faster, dissol e faster and absorb more gas than a similar material with a lower surface area, =e use the :;T e7uation as

';5 P6Po; P7#'Q O 6C#'7 6Po; P7 ; 5m C F'; 5m C

=here N% Nolume of gas adsorbed, P% ;7uilibrium pressure of adsorbent, Po% saturation apour pressure, Nm% monolayer olume of adsorbant,
&< | P a g e

!%:;T constant "inally the Physisorption surface area of the sample is calculated using the formula,

StO5mR:"vR"m;M5
=here

:"v is + agadroUs number "m is the cross%sectional area

M5#molar olume 5m%3umber of moles

N.,-!haracteri8ation of micro structure of the Titanium sample using ?$;M@G

The $canning ;lectron Microscopy and ;nergy Dispersi e +nalysis ?$;MF;D+9@ 5ses electron instead of light to form the image, .t has a ery high resolution than any other techni7ues, >ere this techni7ue is used to determine the microstructure of the titanium sample, The samples were imaged using + Philips 92%*' modal ;lectron microscope with pro ision for ;D+9, This techni7ue is one of the most useful methods for in estigating the microstructure of materials, The electron beam emitted from a heated 2anthanum he/a boride cathode gets focused by a system of magnetic lens ?usually two condenser lenses and one objecti e lens@, +cceleration oltage of 2'KN is used to accelerate the electrons, To
6' | P a g e

generate the re7uired acuum, ion getter pump was used which produces a acuum le el of about 1'%) millibar, The electron beam scans the specimen in much the same way as in cathode ray tube for image formation on the screen, =hen the primary electron interacts with the specimen, electrons and other radiation are produced that can be used to form images and to analy8e chemically the elements present on the surface of the sample, Three modes of operations are secondary electron mode, backscattered electron mode and 9%ray spectroscopy, $econdary electrons are formed by interaction of the primary electrons with loosely bound atomic electrons, .nformation on the chemical composition is obtained by energy dispersi e spectrometry ?;D+9@, 9%rays are produced during de%e/citation of outer electrons into the inner shell acancies of the analyte atoms, These acancies are produced due to the interaction of inner shell electrons with the high energy electron beam, + $i ?2i@ detector was used for detection of 9%ray, The Titanium sample was made into small pellets and was mounted on the sample holder and placed in the analysis chamber of $;M, +fter attaining a acuum le el of 1'%6 torr, the electron beam was impinged on the surface of the diffusion electrode where catalyst was placed, $ince the electrode was ha ing carbon as supporting substrate, conducti e coating was not re7uired, The surface microstructure was studied at arious magnifications and the chemical purity of the catalyst was in estigated by ;D+9,

!>+PT;0,N.. N.., 0esult and discussion

The systematic study of any e/periment will not be fulfilled without discussing its results, The results and discussion are of much importance for the analysis, .t also gi es an interpretation results for internal beha ior of the material structure and its properties,

61 | P a g e

>ence, in this chapter results of studies related to hydrogen sorption capability carried out on titanium samples are discussed, The fresh titanium powder was characteri8ed by 90D, :;T and $;M, "igure1 shows the 90D pattern of fresh titanium powder and the matching with Y!PD$ alues of the sample peaks are alues for Ti, The titanium powder has the ma/imum

peak at -',1' and has the crystal structure of he/agonal closed pack ?>!P@, The chemisorption studies were carried out using TPD04 instrument, The structural and morphological studies of the samples were carried out by 90D, $;M and the surface area measurement by :;T,

1600 1400 1200

101

Intensity

1000 800 600 400 200 0 -200 0 10 20 30 40 50

100 002

Untreated Fresh Titani !

110 102

004 103 112

60

70

80

90

2 theta

&igure))( 3RD pattern for fresh titanium sample

62 | P a g e

TPD04 $tudies
The chemisorption of hydrogen on titanium sample was in estigated instrument, sample, 5>P the argon in for port using +fter TPD04 loading was
sa!"'e si(na'#!)&
550 16000 500 14000 450 12000 10000 8000 6000 4000 2000 0 0 1000 2000 3000 4000 5000

sample at the of some

room pre% time

'

temperature treatment instrument

TPD04

400 + * 425 + * 450 + * 475 + * 500 +

350 300 250 200 150

and then heated to 12( ! to remo e moisture if any in the sample, carry The out sample the was connected to analysis port to hydrogen .n the TP0 sample was
sa!"'e si(na'#!)&
18000 16000 14000 12000 10000 8000 6000 4000 2000 0 -2000 -4000

Ti!e#!in&

&igure).a( hydrogen chemisorption on titanium po*der *ith />>?7>>5C temperature

chemisorption, measurement,

Te!"erat re# %&

600 500

purged with )A >2F+r at the flow rate of 2' sccm, The sample was heated to predetermined temperatures of -''4! to &''4! at fi/ed heating rates, "ig,2*a and 2*b show TP0 profiles of Ti sample as a function of temperature from -''o! to &''o!, .n TP0 graph, the T!D signal ?unit of m+@ ?!'@ and are temperature

400

300

200

100 0 1000 2000 3000 4000 5000

Ti!e#!in&

&igure).#( hydrogen chemisorption on titanium po*der *ith 7>>?8>>5C temperature

ac7uired simultaneously, The temperature profile indicates steady heating

6* | P a g e

Te!"erat re# %&

525 + * 550 + * 600 + * 500 +

pretreated by flushing with

400

and maintaining at the re7uired temperature, The integration of TP0 graph ga e the peak area in mNs, The peak area was con erted to 7uantity of hydrogen from calibration parameters, "rom the graph it ery clear that up%to sample temperature of -'' 4!, there was no hydrogen chemisorption on the titanium powder, =hen temperature was increased to -2(4!, the sample started to chemisorbs hydrogen, The
14000 12000

,ea+ted - antity *. H #!i+r* !*'e/(& 2

10000 8000 6000 4000 2000 0 -2000 400 450 500 550
$

hydr*(en +he!is*r"ti*n#T0,&

600

Te!"erat re# %&

&igure)/( ,uantity of hydrogen reacted on titanium po*der +FmoleEg-

7uantity of hydrogen chemisorbed was estimated by integration of the TP0 graph, The 7uantity of hydrogen chemisorbed by sample as a function of temperature is gi en in the "ig%2-, "ig%2- clearly re eals that the 7uantity of hydrogen chemisorption increases from -2(o! and reaches peak 126*- `molFg at (''o! ?which corresponds to &'A stoichiometry@, alue of

=hen the temperature was increased further to (2( 4!, chemisorption of hydrogen on titanium sample was decreasing to )1*6`molFg, =hen the sample temperature was increased further to ((' 4!, chemisorption of
6- | P a g e

hydrogen started sample &''4! hydrogen capacity "ig 2-, to to &&&)`molFg,

gradually decrease to
2500

500 %

.ncreasing the storage almost

Sa!"'e Si(na' #!)&

500

reduced

1500

450 %
440

460

1000

425 %
420

&*<6`molFg as shown in
500

400 0 0 1000 2000 3000 4000

+fter chemisorption of hydrogen by sample at arious temperatures, the sample was subjected to TPD studies to estimate the 7uantity of hydrogen that is desorbed at the temperature, Desorption
$ample $ignal?mN@

Ti!e#!in&

&igure)7a( Desorption of chemisor#ed hydrogen +/>>?7>>5C-

1&''' 1(''' 1-''' 1*''' 12''' 11''' 1'''' <''' )''' 6''' &''' (''' -''' *''' 2''' 1''' ' %1''' ' 1''' 2''' *''' -'''
4

&2' &'' ()' (&' (-' (2' (''

studies were carried out by purging +r at 2' sccm while sample was carried maintaining at out, the the The

('' ! 4 (2( ! 4 ((' ! 4 &'' !

-)' -&' --' -2' -'' *)' ('''

temperature at which TP0 desorbed hydrogen profile by TPD is shown in "ig, 2(a and 2(b, The 7uantity

Time ?min@

&igure)7#( Desorption of chemisor#ed hydrogen +7>>?8>>5C-

of hydrogen desorbed from the sample was calculated as it was done in TP0, "ig2(a is the desorption cur e in the temperature range -''%(''4! and 2(b is similar cur e in the temperature range (''%&''4!,

6( | P a g e

Temperature? !@

Te!"erat re# $%&

temperature

to

2000

475 %

480

.t is seen that the hydrogen storage capacity of Ti increases steadily with temperature up to (''4! and further increase in temperature bring down the hydrogen storage capacity drastically, "ig,2& shows the hydrogen desorption of
titanium sample at temperature -'' %&'' 4!, .t can be found that the hydrogen

releasing from Ti sample steadily increases with temperature up to &'' 4

8000

,e'eased - antity #!i+r* *. H !*'e/(& 2

7000 6000 5000 4000

Hydr*(en diss*r"ti*n#T01&
3000 2000 1000 0 420 440 460 480 500 520 540
$

560

580

600

620

Te!"erat re# %&

&igure)8( ,uantity of hydrogen released on titanium po*der +FmoleEg-

"ig,26 shows the comparison of TP0 and TPD profiles of hydrogen for Ti, .t is desirable to ha e high chemisorption and less desorption of hydrogen to ha e net hydrogen storage, "rom the graph it is e ident that at temperatures between -2(o! to (''o!, the net storage is high, The net hydrogen storage results obtained by TP0 and TPD studies are gi en in table% 1, The temperature of ('' o! was selected to be optimum to ha e high net hydrogen chemisorption, +t (''o!, the study on repeatability of chemisorption and desorption were carried out and the chemisorption was highly reproducible and is shown in "ig,2),

6& | P a g e

.n this techni7ue, the chemisorption was measured by the amount of hydrogen gas chemisorbed on the gi en sample, .,e, -6,))gFmol of Ti reacts stochiometrically with 2gFmol of >2,

&igure);( +et trappin8 e!!iciency ,uantity of hydrogen on titanium po*der +FmoleEgto form -<,))gFmol of titanium hydride, Therefore 1g of Ti contains

K1gF-6,))gFmoleK2'))(,(`mole of hydrogen,

550 16000 500 14000 450

$

Sa!"'e Si(na'#!)&

400 350 300 250 200 150 100

10000 8000 6000 4000 2000 0 0 1000 2000 3000

4000

5000

Ti!e#!in&

Te!"erat re# %&

12000

500 + * 500 + * 500 + * 500 +

66 | P a g e

&igure.)< 0ydrogen chemisorption on titanium po*der at 7>>5C temperature

$a#le.( trapping efficiency of hydrogen chemisorption on titanium po*der *ith )>5CEM6 on different temperature />>?8>>5c S.+ * 3-IG1 . 6m87 .PR .-M P. 6 *C7 -''4 ! -2(4 ! -('4 ! -6(4 ! (''4 ! (2(4 ! (('4 ! &''4 ! (''4 ! (''4 ! (''4 ! Sty o! 1( reacte 6Tmol;8 7 3.2 )-&' 1'1&& 11'2* 126*)1*6 &&&) &*<6 1'-&< 1'<)) 11666 .rapp e Cty U .PD .-M . * 6 C 7 -''4 ! -2(4 ! -('4 ! -6(4 ! (''4 ! (2(4 ! (('4 ! &''4 ! (''4 ! (''4 ! (''4 ! Sty o! 1( release 6Tmol;87 3.2 66( <&2*&6 (&(6 62((<)()*2 2*&) *1'6 *-&) .rapp e Cty +et trappin8 e!!iciency 6Tmol;87 3.2 6&)(?*&A@ <2'<?--A@ )&(&?-1A@ 6'66?**A@ ))*?-,2A@ &)-?*,2A@ (&(?2,6A@ )1'1?*)A@ 6))1?*6A@ )*'<?*<A@

1 2 * ( & 6 ) < 1' 11

','2)1 ','*'6 ','*'& ','*'','*'','*'6 ','*'1 ','*'1 ','*'2 ','*') ','*'-

''A -'A -)A (2A &1A *)A *1A *'A ('A (2A (&A

''A <A <,-A 21A --A )6A )<A <1A 22A 2)A 2<A

6) | P a g e

?#Ray

i!!raction stu ies on lattice mo i!ication o!

titanium on chemisorption o! hy ro8en

"ig 2< shows the 90D pattern of untreated Ti powder, commercial Ti> 2 and Ti metal with chemisorberd >2, The phase purity of the commercially a ailable titanium powder was in estigated by 90D diffraction measurement, "igure,2< displays the 90D pattern of the sample and all the major reflection can be inde/ed to the titanium phase, which were in e/cellent agreement with the Y!PD$, The crystalline planes and corresponding ?hkl@ alues of titanium are ?11'@,?''2@,?1'1@,?1'2@,?11'@,

?1'*@ and ?2'1@are obser ed, The figure ?<@ also shows the 90D profile of titanium powder with chemisorbed hydrogen, =hen compared with 90D profile of Ti and that of commercial Titanium hydride, it is to be concluded that the some of the peaks in the 90D pattern of Ti with chemisorbed hydrogen correspond to .itanium hy ri es ?Ti>2@ as well as .itanium ?Ti@ phase, The ma/imum intensity peaks, 111 planes correspond to titanium hydride ?Ti> 2@ and ''2 planes corresponds to the titanium ?Ti@, $ince we obser e titanium peaks, we conclude that hydrogen chemisorption on titanium is taking place at the optimi8e le el only,
6< | P a g e

The 90D peaks ga e clear indication of nano si8ed titanium powder, The particle si8eXdU of titanium was estimated by Debye%$cherrerUs e7uation dK',<aF: cos^ =here a is the /% ray wa elength, ^ is the :ragg diffraction angle, and : is the full%width at half ma/imum ?"=>M@ of the peak corresponding to ^, =hen calculate the particle si8e using scherrerUs e7uation, the fresh titanium powder contained the particle si8e of *-nm, but in the case of hydrogen chemisorbed on titanium powder the particle si8e was 2)nm, +t room temperature the metal e/ists as alpha ? V@ titanium and the crystal structure is he/agonal closed pack ?>!P@ and when the titanium powder sample is e/posed to hydrogen, it slowly undergoes reaction and made to titanium hydride and crystal structure changes to "ace !entered !ubic ?"!!@and form beta ?W@ titanium

)' | P a g e

1600

101 Untreated Fresh Titani !#Ti&

Intensity

1200 800 400 0 1600 0 10 20 30

111 100 002

102

110

103 200

40

50

60

70

80

90

Intensity

1200 800 400 0 0 500 400 300 200 100 0 0 10 20 30 40

002 200

+*!!er+ia' Titani ! hydride#TiH 2& 220

311

222

10

20

30
111

40

50

60

70

80

90

Intensity

1ate2 18-4-13 Sa!"'e 2 Ti #030301& ( 1e(2 ,T-125 % .*r 30 !in T0, 2 125-500 % .*r 1 h 4 20 F/!in #5.. 556& 200 220 311

222

50

60

70

80

90

2 theta

&igure)=( comparison of fresh titanium, commercial titanium hydride *ith treated titanium hydride

Physisorption surface area measurement using :;T

)1 | P a g e

The fundamental interaction force of Physisorption is caused by der walls force, ; en through the interaction energy is

an

ery weak ?1'%1''

meN@, Physisorption plays an important role in nature, $ince physical adsorption is an e/othermic process, it occur more readily at lower temperature and decreases with increase in temperature, .n case of Physisorption of gases o er solids, the e/tent of adsorption increases with increase in pressure, The :;T method is based on adsorption of gas on a surface, >ere the adsorption of nitrogen gas on both the sample ?Ti, Ti>2@ surface was determined, The amount of gas adsorbed at a gi en pressure is allows to determines the surface area of the samples, "ig*', *1 shows the :;T plot in which PFP o is plotted against 'EVads +P>EP?'-. "rom the plot, the slope :A+C?'-EVmC- and intercept ?AA'EVmC@ and monolayer olume VmA'E+AG:- were calculated, The olume were obtained to be alues of slope, -,-<< cm %* g, intercept and monolayer

',--1 cm%* g and ',2'2)cm*Fg respecti ely, "rom the monolayer olume the Physisorption surface area was calculated using the e7uation gi en below,

StO5mR:"vR"m;M5
=here :"v is + ogadroUs number, "m is the cross%sectional area, M5#mass of the sample and 5m%3umber of moles, "rom the abo e e7uation, the surface area of titanium powder sample was found to be ',))m2Fg,
4

p/(Vads (p0-p)) / cm-3g

-1

-2 0.0 0.1 0.2

p/p0

0.3

0.4

0.5

0.6

)2 | P a g e

&igure.>( :C$ result for titanium

0.5

0.4

p/(Vads (p0-p)) / cm-3g

0.3

0.2

0.1

0.0

0.1

0.2

p/p0

0.3

0.4

0.5

0.6

&igure.'( :C$ result for titanium hydride

Table ?-@ shows the measurements of Physisorption surface area of the titanium and titanium hydrides powder, There is much difference found between surface area of titanium ?',))@ and titanium hydride ?),)2@, The graphs 1 and 2 were obtained from the two samples ?Ti, Ti>2@, The graphs were obtained by plotting PF ?Nads?P4%P@ Ns ?PFPo@ and a straight line is e/pected, "rom the graphs we obser e that the e/tent of adsorption increases with increase in pressure,

$a#le/( Measurement of Physisorption surface area using :C$

$ample

$ample wt?g@

Physisorption surface area ?m2Fg@

Titanium Titanium hydride

1,(-(( 1,6-2*

',)) ),2)

)* | P a g e

$;M Measurement
+fter the chemisorption of hydrogen on Ti powder by TP0, the sample was characteri8ed by $;M for studying surface morphology, $ince powder samples cannot be handled in the $;M instrument, the sample was pellatised, The $;M image of Ti with chemisorbed hydrogen ?Ti> 2@ is shown in the "ig *2, "rom the "ig it is obser ed that particles si8e is around 2'%*' nm, Particle si8e was also estimated by 9%0ay diffraction using $cherrer e7uation, The particle si8e for Ti> 2 formed by TP0 was 2) nm which was in agreement with $;M results, >owe er, due to the pelleti8ation some regions in the samples were obser ed to ha e flattened surface e en for highest resolution,

&igure .)( SCM image of hydrogen chemisor#ed $itanium +$i0)-

)- | P a g e

C+a9ter III
Summary an conclusion

The earlier studies done in this field pro ided remarkable opportunities for the research on the subject as it is an acti e field of research in which new in estigation are currently being carried out, The literature sur ey done by the author re iews the work done in the field of hydrogen chemisorptionF desorption, .t has created a thirst to research scholars to know more about chemisorption beha ior of metals and its applications, The present study is mainly focused on the hydrogen

chemisorptionFdesorption on Ti powder samples by TP0 and TPD methods, The optimum temperature for hydrogen storage on the samples was established and the parameters will be of great importance in storing hydrogen produced from industrial processes, +t the gi en parameters, the ma/imum storing capacity of hydrogen in titanium powder samples were demonstrated and was found to be 11( g of hydrogen per litre of titanium sample which is in ery good agreement with literature alues and the storage capacity is obser ed to be similar to that of li7uid hydrogen, The titanium before and after chemisorption were characteri8ed by 90D, :;T and $;M techni7ues for its structure, morphology and surface area, The structural studies with 90D shows a ery sharp peak for fresh

Titanium and broad peak for Titanium chemisorbed hydrogen ?Ti> 2@, 3o peaks of impurities are detected, The 90D pattern is good agreement with the Y!PD$ and the particle si8e calculated from the 90D pattern is found to be of b*' nm
)( | P a g e

The surface area measurement for the "resh Titanium and hydrogen chemisorbed Titanium ?Ti>2@ sample using :;T is studied and the measurement of surface area is found to be for Titanium ?',)) m 2Fg@ and Titanium hydride ?),)2m2Fg@ due to the high surface area in the Titanium hydride,

)& | P a g e

0eference
1, 2ight metal hydrides for re ersible hydrogen storage application, Yianfeng Mao uni ersity of =ollongong, 2, =orld business council for sustainable de elopment,?2''-@ #ene a, $wit8erland, + ailable an, 2ine atG www, =bcsd, 4rg *, The impact of fuel economics regulation in .ndia, uni ersity of Maryland, college park department of economics,?2'1'@ on Eline at G www,nscw, ;duFcerrepFworkshopsF documentsFchugh%comporesources, Pdf -, ;nergy and transportation science di ision ?;T$D@ on% line at

www,ornl,go ,?2'1*@ (, >ydrogen based ehicalee research initiati e is making, on line at

www, 0enewable energy world, !om?2'')@ &, 5,s department of energy hydrogen program 2''& annual merit re iew proceedings, technology,www, >ydrogen energy, #o economy, #o 6, 3, 3, #reenwood, +, ;arnshaw, C!hemistry of the ;lementsD, 4/fordB :oston, :utterworth%>einemann ?1<<6@, ), CThe >ydrogen ;conomyG 4pportunities, !osts, :arriers, and 01D 3eeds, !ommittee on +lternati es and $trategies for "uture >ydrogen Production and 5seD,3ational 0esearch !ouncil, 3ational +cademy of ;ngineering, 3ational +cademy of$ciences, and www, "uel

<, T,3 e 8iroglu, .nt,j ,hydrogen energy 2'?1<<(@,

)6 | P a g e

1', energy

>ydrohen economy and alternati e fuel, Published on iee.;;; technology postal 2''&%2'11,

>ttyGFFwww,ieee,orgFgoFemergingtech, 11, >ydrogen economyG its historyGB john oUm, bockrisB olume *),

issue &, 26feb 2'1*, pages2(6<%2()) 12, Timothy lipmanB hydrogen production and storage%.nternational +gencyB !lean energy ststes +lliance?2'11@,website

;nergy

www,ie,orgFpublication 1*, !ohen,m and g,c,snow?2'')@ hydrogen deli ery and storage

options for backup power and off%guid primery power fuel cell systemUs published in .;;; intebe 2'') proceeedings, 1-, 2ife cycle assessment of arious hydrogen production methods ;,

!etinkaga, .,Dincer, #,",3aterer, .nternational journal for hydrogen economy,*6?**@,P2'61%2')', "eb%2'12 1(, >ydrogen energy% abundant, efficient, cleanB a debate o er the

energy Esystem of changeB corl%jochen winterGB*-?2''<@ $1%$(2 1&, Progress and problems in hydrogen storage methodsB 2i VhouB

<?2''(@ *<(%-'), 16, 4 er iew of hydrogen storage technologies :rian D YamesB

Directed technologies,inc,-''1 north "airfa/ dri e $uit 66(,+rlington Na,222'*, 1), Materials for hydrogen storageG current research trends and an den berg,,, and carbsotero +rean,,

perspecti esB annemiekeew,c, www,rsc,orgFchemcomm

published as an ad ance on the web 1& th 4ctober 2''6 websit

)) | P a g e

1<,

De elopment of +utomoti e 2i7uid hydrogen $torage systemsG #,

Krain8, #, :arlot, p, :odner, P, !asapicola, ch,, >allar,,, ", >ofmeister,, ;, 3ewbacher,, +,,, Vieger, M+#3+%$T;N0 "ahr8engtechnik +# c !o K# +%)'-1 #ra8, +wstric 2', >igh capacity hydrogen storage materialsG attributes for

automoti e application and techni7ues for materials disco eryG% Yum yang, +ndrea $udik, !hristopher wol erton and Denaid j, siegel published as an +d ance article on the wet 1- th $eptember 2''<B D4.G% 1',1'*<Fb)'2))2f, 21, httpGFFwwwF, ;rre, ;nergy go Fhydrogen and fuel cellsF

storageFpdfsF targets% enboard%hydro%storage% e/planation,pdf 22, Targets for onboard hydrogen storage systems for light%duty ehicles% 5$ Department of energy $eptember 2''<G% website

www,hydrogen storage target 2*, The 5$ Departmetn of ;nergyUs 3ational hydrogen $torage future plansG% $unita

ProjectG% #oals, progress and Yohn PetraicG% >onolulo, >1 , +pril 2&%26,2''6 2-,

$atyapal, !arde 0ead, #rance 4rda8, 3ed $tepson, #eorge Thomas,

2ide, D, 0,, !0! >andbook of !hemistry and Physics ?6&th ;d,@,

3ew ZorkG !0! Press, ?1<<(@, 2(, "roes, ", >,, ;ylon, D,, 1 :omberger, >, :,, Titanium technologyG

present status and future trends, Dayton, 4hioG Titanium De elopment +ssociation, ?1<)(@,
2&,\Titanium\, !olumbia ;ncyclopedia ?&th edition ;d,@, 3ew ZorkG !olumbia 5ni ersity Press, ?2'''E2''&@, .$:3 '%6)6&%('1(%*,

26,

Matthew Y, Donachie, TitaniumG + Technical #uide, 2nd ;dition,

p(%11, +$M internationald, Materials Park, ?2'''@,

)< | P a g e

2),

#erd 2utiering, Yames ! =illiams, engineering materials and

processingG titanium, second edition, $pringer publications, ?2''6@, 2<, :oyer, 0,, 3ew Titanium +pplications on the :oeing%666 +irplane,

Yom%Yournal of the Minerals Metals 1 Materials $ociety, --?(@, 2*%2(, ?1<<2@, *', $chut8, 0, =,, 1 =atkins, >, :,, 0ecent de elopments in titanium

alloy application in the energy industry, Materials $cience and ;ngineering a $tructural Materials Properties Microstructure and Processing, 2-*?1%2@, *'(%*1(, ?1<<)@, *1, "roes, ", >,, +llen, P, #,, 1 3iinomi, M,, 3on%aerospace

applications of titanium, =arrendale, Pa,G TM$, ?1<<)@, *2, #asser, 0,P,>1<)(@ + introduction to chemisorption and

catalysis by metals, clarendon press, 4/ford, **, K, oura C$urface science, +n introductionD :erlin, $pringer, .$:3

<6)%*%(-'%''(-(%2,2''*, *-, M,$, Desjon7ueres, C concepts in surface physicsD, $pringer% erlag, .$:3,<6)%'%*'6 (&('&%-, 1<<*, *(, !,T, 0ettner, D, Y, +uerbach, C !hemical Dynami<cs at the #as%

$urfaces interfaceD Yournal of Physical chemistry, Nol,1'',pp,1*'21% 1*'**, 1<<&, *&, K, oura, N,#,2ifshits, +,+ sarnin, +,N, Voto ,M, Katayama,

C$urface $cience, +n .ntroudction :erlin, $pringer, 2''*, *6, >,2oth, C$urfaces and interfaces of $olidsD, $pringer% erlag, .$:3

<6)%*%(-'%(&)-'%6,1<<( *), ;, Varemba and =, Kohn, CTheory of helium adsorption on

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