ARMED SERVICES TECHNICAL INFORMATION ...(Na 2O-2V20 5), sodium sulfate (Na2SO4), calcium sulfate...

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N••L Report 5852

:; -AR URVEY OF THE CHEMISTRY OF HIGH-VAlADIUM" "4 OIL-ASH DEPOSITS IN NAVAL BOILERS

A. J. Pollard

Physical Metallurgy BranchMetallurgy Division

November 19, 1962 ,

p ".Z•

6 ASTIA Ii

i'5, , ,

U. S. NAVAL RESEARCH LABORATORYWashington. D.C.

0 2'.'

J .""r

CONTENTS

Abstract illProblem Status titAuthorization iii

PART IPROPERTIES OF VANADIUM OIL-ASH DEPOSITS

AND THEIR OXIDE COMPONENTS

INTRODUCTION 1

THE PHYSICAL NATURE OF OIL-A'H DEPOSITS I

THE MICROSCOPIC NATURE OF OIL-ASH DEPOSITS 1

THE CHEMICAL NATURE OF OIL-ASH DEPOSITS 3

THE DISTRIBUTION OF CHEMICAL COMPOUNDS WITHIN BOILERS 3

Compounds on Screen Tubes and Superheater Tubes 3Compounds on Generating Tubes, Economizer Tubes, and the

Top Surfaces of Water Drums 4

Compounds in Uptakes, Breeching, and Stacks 4Miscellaneous Compounds Occurring in Minor Percentages 4 ,

THE CHEMISTRY OF VANADIUM COMPOUNDS IN OIL-ASH DEPOSITS 4

General Considerations 4High-Temperature Properties o0 Systems Containing Sodium

and Vanadium Ox ides 0High-Temperature Properties of Systems Containing Oxides of

Other Elements in Addition to Sodium and Vanadium Oxides 9Systems Containing Vanadium Oxides and Other Metal Oxides 9Room Temperature Reactions of Compounds Formed

at High Tcmperaturrs 9 t,

AREAS IN WHICH FURTHER BASIC RESEARCH WOULD BEOF IMMEDIATE VALUE 9

PART 2SPECIAL LABORATORY METHODS USED

IN THESE INVESTIGATIONS

S rANDARD X-RAY PATTERNS OF COMPOUNDS DETECTEDIN HIGH-VANADIUM OIL ASH AND THEIR SIGNIFICANCES 11

ValldIunt Comnpounds (Table 2) 11 P•'"43) 13 sSodium Sul!ate (T"ahleý 3)13*,'a

Calcium Sulfate (TAilt., 4) 14Silica (Table 5) 15Iron Compounds (Tahle 6) 15Carbon 18 e

PROCEDURE FOR THE DIRECT GRAVIMETRIC ANALYSIS OFHIGH PERCENTAGES OF VANADIUM IN OIL ASH 17

I '-I

CONTENTS (Continued)

ANALYSIS OF HIGH PERCENTAGES OF VANADIUM INOIL ASH USING X-RAY FLUORESCENCE TECHNIQUES 18

The Estimation of Vanadium by the Measurement ofChromium K: Absorption (Method 1) 18

The Direct Measurement of Vanadium SecondaryRadiation as a Means of Estimating Vanadium _

Content of Oil Ash (Method 2) 19

THE QUANTITATIVE ANALYSIS OF CRYSTALLINE Na:O'V2 OV'O5VgOgand Na 2O'2V2 O5 YN THE PRLSENCE OF ONE ANOTHER USINGX-RAY POWDER DIFFRACTION METHODS 19

ACKNOWLEDGMENTS 21

REFERENCLS 22

APPENDIX A - Sourr-s of Data on Systems ContainingVanadium O..ides 23

ADDITIONAL SELEC i"FD BIBLIOGRAPHY USED BY AUTHORiN HIS \VORX 32

A

N,

4 ,i

* ,~* 3 I :

ABSTRACT

High-vanadium oil-ash deposits taken from the boilers ofdestroyers andcarriershave been examined anda survey madeof the c h e nm i st ry of their components. Three conmpoundsofvanadium were identified: Na*O.V 2 04-5V2OC, which appearedin every high-temperature deposit examined, and Ma O'2VI OSand NaVOs. both of which we-re found only on screen tubes oftwo 1200-pound boilers having deposits especially high in sodiumsulfate. Other compounds present in detectable quantities wereNaSOS4 ,CaSO 4 , FC3 O 4 , CaCO3, Fez(SO4 ),, H2SO 4 , a-SiO,, andelemental .arbon. All deposits consisted ot one or more ofthese compounds, but in various proportions.

The .hemistry and physical properties of compounds in thesystem NaxO-VxOswere compiled after a literature searchwhich was augmented by an appro)priate laboratory investigation.Compilations were made of sources of information on systemscontaining vanadium oxides and the oxides of other elements,useful for the ident ification of the crystalline components of oil-ash deposits.

Three analyt ical methods for the determinationof highconcentrations of vanadium in oxide mixtures are described,as well as an x-ray diffraction method for estimatingthe rela-tive quantities of crystalline Na 2 OV 2 0l-fVO and Na2 O.2V20,in the presence of one another.

Some areas of research of prod)able immediate value towardsolving the oil-ash deposition and corrosion problems are phasestudies, sintering studies, and development of chemical cleaning|)r otesses.

PROBLEM STATUS

This is an interim report. Work on this problem iscontinuing.

AUTHORIZATION

NRL Problem MOl-08Project Sit 007-08-08-0624

l.,winc ript stubmittedrl S&pteritbIer 14, 196Z.

lit

A SURVEY OF THE CHEMISTRY OF HIGH-VANADIUMOIL-ASH DEPOSITS IN NAVAL BOILERS

PART I - PROPERTIES OF VANADIUM OIL-ASH DEPOSITSAND THEIR OXIDE COMPONENTS

INTRODUCTION

The deposition of noncombustible matter on the heat-exchange surfaces of navalboilers is a serious problem. Not only are the deposits objectionable due to their rela-tively poor heat-transfer properties, but they may be extremely corrosive in locationswhere temperatures are above the melting point of the ash. Removal of deposits, onceformed, may be all but impossible by ships' personnel, and complete retubing in repairyards is occasionally preferred to manual cleaning methods, because the ultimate costand effort may be less.

The present work was intended to be a critical examination of the problem. It con-sisted of a thorough search of the scientific and engineering literature; visits to shipsknown to have had oil-ash problems, and to similar ships which did not; the collection ofspecimens firsthand; the analysis of specimens' and identification of components by chemi-cal and physical methods; discussionkof the problem with shipyard maintenance workers,type commanders, ships' personnel, and shipyard laboratory personnel; and laboratoryexamination of chemical reactions in systems thought to represe-t those met in theboilers proper.

THE PHYSICAL NATURE OF OIL-ASH DEPOSITS

A portion of the incombustible matter originating in the fuel which is atomized intothe combustion zones of naval steam boilers accumulates on.the upstream surfaces oftubes which cross the gas stream. After prolonged operation of boilers a thin coating ofhard, high-vanadium ash of the order of 1/8-inch thick is quite common on the surfacesoi superheater tubes, although accumulations are occasionally massive and may causeblockage of gas passages. By far the greatest proportion of solid matter in oil passesthrough the boilers and, fortunately, out through the stacks.

The heaviest accumulations of debris occur in the economizers and on the top sur-faces of water drums, and both of these areas require special treatment for the removalof foreign material. That which adheres to economizer tubes is removed by means ofsoot blowers during the operation of the boilers, and the water-drum deposits are removedby chemical and phyr-i cal methods during maintenance outages.

Physically, water-drum and economizer deposits are similar, being for the mostpart earthy masses of material, quite different from the typical high-temperature depositsof thc superheaters and screen tubes, which are almost vitreous in nature. There isnearly always a vitreous layer of high-vanadium content, however, near the surfaces ofthe generating tubes over the water drums, but this is usually buried beneath largeamounts of loosely bfound and less homogeneous material.

THE MICROSCOPIC INATURE OF OIL-ASH DEPOSITS

Portions of oil-ash deposit which are soft and crumbly are composed of randomparticles of more or less pure compounds concentrated in clusters. The vitreous, nearly

I

2 NAVAL RESEARCH LABORATORY

Fig. I - Crystals of Na 2 O.V 2 O 4 -5V2 O$ making up .black vitreouslayer of oil ash. Reflected polarized light 75X.

black layers of material which are notoriously difficult to remove are composedof large, intermeshed crystals of Na .O• V04"Va Os, which act as a ceramic bond for thehard layers. Other cry.s.talline materials present In the hard layers can be observed assmall particles enmeshed in a matrix of long needles of the vanadium compound (Fig. 1).In spite of the extreme hardness of these layers, the structure is not dense, and water-soluble fractions can be e:,tractec' from the interior regions of the deposits withoutnoticeably affecting the hardness or disturbing the ceramic bonding of the layers.

From the fact that the longest, most perfectly developed crystals are consistentlylocated in an intermediate position between the innermost layers of the deposit and theoutermost surface it was concluded that these crystals are secondary in nature, not beingdue to crystallization of a melted mass, nor to the accumulation of material alreadycrystallized. Many fernlike groths of Na 2 O-VN0 4 "5V2 0s canbe observed with their pointsof origin toward th," hot side, and radiating inward toward the cooler tube surfaces. Someof these can be traced over a distance of at least 1/4 of an inch, a fact which favors theconclusion that extensive crystal growth may have occurred after the deposits hadaccumulated.

NAVAL RESEARCH LABORATORY 3

THE CHEMICAL NATURE OF OIL-ASH DEPOSITS

The chemical compouJnds Isolated and identified In this investigation were as follows:ii-sodiunm-vandium oxide [Na 2 0.V, 04 5V, Os (approximately)), -f-sodium -vanadium oxide(Na 2O-2V20 5), sodium sulfate (Na 2SO4), calcium sulfate (CaSO4), magnetite (Fe2O4),c-alcuium carbonate (CaCO 3), ferric sulfate [Fe,(S04 )3]. elemental carbon, sulfuric acid(H2S0 4), and a-cristobalitc (a-SiOa). All deposits consisted of one or more of these com-pounds, but in various proportions.

There were, in addition to these idntified compounds, traces of zinc, considerablequantities of nickel (as much as 1.45% In high-vanadium ash), and traces of manganeseand titanium, all of which were detected hat not Isolated as solid compounds.

The p~robable sources of these compounds are as follows: vanadium compounds,fromi fuel oil; sodium comphlounds, [ronm fuel oil or from ballast sea water via the burners,or front salt spray arriving with combustion air; calcium compounds, from fuel oil, wherethey may lie present as calcium carbonate or sulfate, or from sea water (in flue gas athigh temperatures ralcium carbonate Lccornes calcium sulfate); iron compounds, mostlyfronm rorrosion of structural components, but small amounts are present In fuel oil;sulfui compounds, fronm fuel oil; silicon dioxide, from fuel oil, where it is in suspension,sea water, or Ironm the atmosphere during operation In proximity to shore; and nickel and.mnganciisL comipounds, from fuel oil and corrosion products of high alloy steel.

It should he noted that chromitim was not dletected, even In minute traces. This ele-tuent is lto bu expected in the corrosion produIý,ts of stainless steels used in naval boilers.

The chemiviistry of all the compounds listed, other than that of sodium-vanadium oxides,is couvrud in moist elemtentary chemistry texts. No mention of sodium-vanadium oxides(if the sort encountered in oil ash was found in any standard reference book, however, andgreat effort was cxpuiidccl in ordi r to locate details concerning the sodium-vanadium oxides~ysteml in] the chrm11iral liternture-. For this reason the system is discussed separately

THE DISTRItIBUTION O F CHIIEM1ICA L COM POUNDS WITHIN BOILERS

The iehenicatt and p~hysical environments tio which oil ash Is exposed within boilersvary over wide rariges, and the compounds obiserved in slag samples taken from super-heater tubies dilker considerably from those %%hich are found In cooler regions of boilers.There are iriatav coimsistencies, holwever, as lei the compounds which are found in equivalentbeaittil.ns ot (different boilecrs.

Comlot' iinds oni Stcrevin *ubt ., awl Sipt rheater Tubes

The vctrIonareew'is. black d. pisits of the hiterior of furnaces are for the most partaanorpt.ims t arl)(a, ;iithou,u-la the r'' is often graphitization, which can be detected by x-rayditfrart~itL niethEos. Thi- winte'riati Is ic(tualIIy unlburned oil, and presumably accumulateswhen flif, liurn1-rs- are 4cut o'ut.

Chalky whlet, water- slUl('l iafttrHal coating the screen tubes, and which is sometimeshiddf i by vrhirni, is utsuailly eithwr so'dium stiilfate, or a mixture of sodium sulfate withSOCIditi. vniaiirkttc. (Material -ontaijnint:" srmditin vatnadalt, gives an alkaline solution withwat( r, whi~q hes irdum sahI.Ot. is nieut ral.)

I Ili rple-hiwk k Ia rs mli scruvit tubes andl superheater tubes arc invariably composedNa N'i'" 2 041 VNO1 . soliletinics miixed wikith small :iniounts of N:I 0O2V, O* or sodium


sulfate. These layers are the most difficult to remove by present cleaning methods ifthey are tightly bonded to the metallic surfaces because they are not appreciably solublein water and dilute acids. This is also the material which, when molten, is an excellentsolvent for most materials of construction of boilers.

Compounds on Generating Tubes, Economizer Tubes,and the Top Surfaces of Water Drums

Generating-tube deposits are similar to superheater dpoosits in chemical composition,but show fewer signs of high-temperature effects. There are seldom indications of com-plete melting and flow. Compounds us,-ally found are sodium sulfate, Na2O.V 3 O4 .5V 2O$,and sometimes small amounts of Na.O-2V&O,. Next to tube surfaces there is usually asmall amount of white ferrous sulfate, which turns yellow (ferric sulfate) on being exposedto the air. Such deposits give an acid reaction on being treated with water.

The troublesome massive deposits which have been observed on the top surfaces ofwater drums are almost identical to those which accumulate on the fins of economizirtubes. The earthy material which yields to water washing is usually high in sodium andiron sulfates, while the purple-black layers In close proximity to tubes where they enterthe drum and the powdery residue from water washing are almost entirely identical withthe shell-like layers taken from superheater and screen tubes, i.e., they are mostlyNa2O'V. O, 5VOS

Compounds in Uptakes, Breeching, and Stacks

In general, it can be stated that dustlike material deposits in gas passages beyond theboilers, and that liquid sulfuric acid accumulates when the temperature of the gas streamfalls below a certain minimum value which is dependent on the firing procedures. Thedustlike material is usually noncrystalline, and aside from a high percentage of adsorbedsulfuric acid, is essentially composed of unburned carbon.

The sulfuric acid may contain sufficient sulfate to qualify as Ofuming sulfuric acid'while the boilers are operating, but this rapidly changes to the highly corrosive dilutesulfuric acid on long standing, or under the influence of a blast of moist air from theblowers when the boilers are down. Invariably, the corrosion products from ductwork canbe found as water-soluble sulfates and water-insoluble spinels on the surfaces of corrodedmetal.

Miscellaneous Compounds Occurring in Minor Percentages

The following compounds have been found distributed at random in trace amounts innaval boiler deposits: silica (a-cristobalite); magnetite (Fe$04), presumably a high temper-ature corrosion product; and calcium sulfate (Cas.e). Calcium carbonate has been foundin water-drum and economizer deposits in trace amounts.

THE CHEMISTRY OF VANADIUM COMPOUNDS

IN OIL-ASH DEPOSITS

General Considerat ions

Choice of a single phase diagram which truly represents the state of vanadium underboiler-operating conditions Is difflcult because or the complexity of the environment Inwhic the oil ash is found. Three compounds or vanadium have been isolated and identified

NAVAL RESEARCH LASORATORY 5

in this laboratory, the compound Na3O.V 2 0 4 .5V206 appearing in every boiler examined,and NazO'2V20% and NaVOj appearing on screen tubes of two 1200-pound boilers havingdeposits especially high in sodium sulfate. It is concluded, therefore, that the systemNa 20-V, 05 should include most of the compounds of vanadium appearing in oil ash of thetypes studied to date, and since it had been found that sodium sulfate loses sulfur andoxygen on being heated with vanadium pentoxide, the ternary oxide diagram,Na.O-V.0, -SOs , would explain most of the thermal behavior of oil-ash compounds. Useof the ternary oxide diagram would be complicated, however, by the fact that some of thepentavalent vanadium is reduced to tetravalent vanadium merely by being heated with anappropriate quantity of sodium oxide, ard by the fact that sulfur trioxide dissociates intosulfur dioxide and oxygen in the presence of certain catalysts, especially the vanadiumoxides containing sodium. For practical purposes, therefore, the phase diagrams of thesystems VzO-NaVO3 and V2 0$-Na2 SO 4 as given by Illarionov (1) are being used at thistime for the interpretation of effects observed during the study of oil-ash deposits (Figs.2 and 3). Neither is claimed to be an equilibrium diagram, but each is based on experi-mental data obtained by heating mixtures of pure starting materials in the presence of air.

Sooo i i ' I "

700-60

700 67. '656 '

.6- 6. \Fig. 2 - Phase diagram for the system

.. AVO•3 - V2O(5I) 96 H 83o

400 - I

"-1/k O2LOST AT3O5 -I I I 1 -1 ! 1 1 1

30 10 20 30 40 50 60 70 80 90 100V205 0 NaVO 3(MOLE% VO3

900 I I I I I.o.

S/800

W

~ 70 6GOO&8 25% *80C ,so - _ 1- ,,5. I _

v-- ss .9%12.1%

-600

55010 10 20 30 40 150 60 70 60 90 100V2 05 No2 SQ4 IN mix (MMLE W) ftt$0

Fig. 3 - PhasLe diagram for the systemNit SO 4 -V2 Oaq (Obtained 1 ro m heatingcurves. Syntins liit at equilibrium.) (1)


High-Temperature Properties or Systems ContainingSodium and Vanadium Oxides

Melting and Sintering Characteristics - When a mixture containing sodium vanadateand vanadium pentoxide is heated, a reaction in the solid state occurs at 265°C (5090 F)and a compound containing 65 mole percent NaVO, forms. To this compound may begiven the formula NazO'2VaOs;* (See Fig. 2).

If the temperature is raised further to 350 0 C (662"F) a second reaction occurs in thesolid state. The NazO-2V0 5 which first formed reacts with any excess of VXO toform a new compound, Na.O.V 2O4.5V,0 3 . The second reaction is accompanied by a lossof oxygen.

The melting points of compounds in this system are: V2Os , 6700 C (1238 0 F);NaaO0VO,'4 5VOs , 738"C (1360°F); NaO-2V,0., 614"C (11370 F); and NaVO., 627°C(1160- F).

The melting points of eutectics in this system, which are the temperatures at whvh,.hinitial melting begins in the presence of two compounds, are as follows: between V.O,and NaO-V O 4 "5V2 OS, 655"C (1212" F); between Na.O-VgO 4 .5V Os and NaO.2VO 5 ,579 C (10740F); and between Na 2O-2V2Os and NaVO3,, 530*C (986°F).

Melting and Sintering Characteristics in the Presence of Sulfates - The systemNaSO4 -V2Os (Fig. 3) differs from the system NaVOs-VsOs in that transition points andeutectic points are displaced. Phases equivalent to NaO.2V 5Os and NaVO2 do not appearin this system. The phase Na20-VsO4-5V 2 08 , which also appeared in systems withoutsulfate, crystallizes with small amounts of sulfate in a form which shows only slightchanges in lattice parameter from the sulfate-free crystals, these changes being detectableonly by precision x-ray methods.

In this system the compound Na.O'V 0 4"5V, 0 5 (with sulfate) melts at about 6800 C

(12560F), the mixture not being at equilibrium. The eutectic temperatures are as follows:between VaOs and NaO-V3O4-g5V2O , 630°C (1i66*F), and between Na2O.V20 4 .5VOBand NaSO4 , 650 0 C (1202'F).

When a mix containing NaS0 4 and V2.0 is heated, a solid state reaction begins at526°C (9780F) with the loss of s03 and oxygen and the formation of Na 2 O'V0O4.5V2 O0(with bulfate).

To summarize the differences between the behavior of mixtures which contained,Initially, NaVO,3, as opposed to NaSO4 , the presence of sulfate tends to raise the tem-perature at which the solid state reaction to form Na.O'V,0 4 5VO occurs, while loweringthe temperature at which initial melting occurs. The final melting occurs at a lowertemperature in the presence of sulfate.

Electrical Prop__rt ies of Sysýtms Containing Sodium and Vanadium Oxides - Thepaper of Flood a'n-dsotrun (3-Y -announced the discovery of a new type of electrical semi-conductor, namely the 'Il-phase" in the system sodium-vanadium oxide. It had been foundin this laboratory that fused mixtures of sodium-vanadium salts are good conductors, butfromn the work of Flood and Sorum it is apparent that the solid compounds are conductors,also. The maximum conductivity at room temperature is of the order of ten percent ofthat of graphite, or is nearly equivalent to that of iron oxide (Fe,0 4 ). (See Table 1.)

I he fi ,),'1,l,, giv,. by Fomte'r et al. (0) is Nga3 O.3Vg0, but this Is based on x-ray data;hlunn, as oppm)it dI to ,mI he,-vitda NaSO*.VgOs of Illarionov (1) which is based onther-


Table 1Table of Electrical Conductivities

M ConductivityMaterial (ohm-' cm-)

NasO"V20 4" 5V208 60

Tungsten Bronze 10

Vanadium Pentoxide 10-3

Magnetite (FeM0 4 ) 100

Lead Sulfide 10 - 100

Graphite 800

The maximum conductivity in the system sodium vanadate-vanadium pentoxide occursin the mixture which is lowest in oxygen content, which also coincides with the composi-tion of NajO-V 2 0 4-5V 20 (see Fig. 4). Flood and Sorum compared this compound withtungsten bronze, and suggested that it is a semiconductor for the same reasons thatmagnetite and tungsten bronze are semiconductors. (Details in the crystal structure ofthe so-called *vanadium bronzes' are reported by Wadsley (4).)

60

.4

60

i£

30

20

IC0-

1.0 2.0 3.0 4.0 5.0

N4o20 (WEICHT %)

Fig. 4 - Elctrical titiductivity as a functionof so,! tjrn Cofit,.nt ill tlt sy.t,.m Na 3 0-V 1 O.(3)

- - - - - - - - -


'he Evolution of Gases on Heating of Solids and Cooling of Melts - The formation ofthe Na2O.V2O4'5V 2 O5 in the system sodium vanadate-vanadium pentoxide is accompaniedby the evolution of oxygen. According to the work of Flood and Serum (3) the ccrnpositionat which the greatest volume is evolved coincides with that of the stoichlonietric compoundNal!O-Va 0 4 5V2 Oz, which was descrlb-ri above as having the greatvst conduictivity and thehigheet melting point In the system NaVO., -V, 05. A graph of oxygen evolution comparedwith composition of the mix Is shown in Fig. 5. The data have been verified by Ullarionov(1) and have heei- shown by both flood and Illarionov to be related to the oxidation stateof the vanadium -emaining behind in the solid.

.9 - Nd2 0.3V5V2 0

N.20.2V2 0100

0

0 5 20 26 N 50

N120 IN W~rUPE (NV0,+V~j CW~tGNT%

Fijn. 5 -Oxygen tcvol it im as alfunct ion of sodiumncontent of incits cont01i~nig sodium and vanadium

N Gises are evolved the first time rnLxtuvvs of vanadium pentoxidc- and, sodium salts of.ýtXZ Mvolatile acids are heated to the melting point. On cooling, additional gases are evolved.

This phenomenon wai, studied in detail in I J08 by Prandtl (5). One of his conclusions was ,that the spittingl must be due to the evolution of oxygen, since a portion of the vanadiuln

in hL Soid ýn Ienruducedtoheeraau st.

A very brief I atbralory investigation on systems containing vanadium pentoxide,initially, aind salts of ~;iodiuni containing anions whic-h are volatile at elevnted temperatures ?~

*.InldiV.ated that the compound Na2G'V30O-5VjOs results when the proper proportioms ot theA'V 'iio~Ing sodiu-coiitauiinK compoundis art' heated wvith vanadium pentoxid-e: sodium

peroxide (Na2O2); sdiumi varbotiate {NaCO1), sodium chloride (NaCI), sodium esulfrte(NaSO4j), sodxium hromidkv (Nal~r), and sodiium vanadate (NaIV03). The gas which wasmiissing trumi the !inal solids wa.s evolved during reactions in the nolid state and Imneiec-

-N ~~atciv after resol idif(-at ion, at which timie (lie solid mavterial remelted with effervesce~nce,an~d itivc recrystallizedl. A qualitative tcest o( the gmsssoe h rsneo ~yciron- &odium peroxidt., varbon dioxide from scdium carbonate; sulfur dioxide, sulfur

'.9 trioxide, aInd oxvgen Irtim ,4Adium slt~ite; andi the gases chlorine an-d bromine from the *>i-orcsondngc'hloride and brom ide reart ions. No gas v'as evolved on solidification after

01C mv'itilng o'. pure Na20VOV, 0450) kinidt v?.cuum a


High-Temperature Properties of Systems Containing Oxidesof Other Elements In Addition to Sodium and Vanadium Oxides

From the standpoint of usefulness in the prediction of the chemical effects of addi-tives a knowledge of compounds formed between the vanadium compounds found in oil ashand the oxides of potential additives would be extremely valuable. The literature searchrevealed that very little work has been done in this area, in spite of the vast number ofpatents issued and the papers written on the subject of additives.

Systems Containing Vanadium Oxides and Other Metal Oxides

Data concerning the systems containing vanadium oxides and other metal oxides arescattered throughout the literature. An attempt has been made to compile sources ofinformation in Appendix A.

In general, it may be stated that pentavalent vanadium oxide behaves as an acid in itsproperties (relative to silica) and that the more basic the oxide with which it is reacting,the greater is the tendency toward compound formation. There is little or no reactionbetween silica and vanadium pentoxide, nor between boron trioxide and vanadium pentoxide.

Trivalent vanadium forms spinels with the same oxides as iron oxide or aluminumoxide. [Most of the reactions of tetravalent vanadium listed In Appendix A were takenfrom a single paper (6) which gives data in direct conflict with other papers on the samesubject. I In all cases reported, the melting points of reduced oxides containing vanadiumare considerably higher than those in which the vanadium is in the pentavalent state.

Room Temperature Reactions of Compounds Formedat High Temperatures

Although vanadium pentoxide and sodium vanadate have appreciable solubility In waterat room temperature, the two compounds which can be formed from mixtures of the two,that is NalO'V2 04-5V.O0 and Na2O'2V2 Om , are only slightly soluble in water. Thesecompounds are quite soluble in hot, concentrated hydrochloric acid, forming first a deepred solution which turns green on standing. The final state of the vanadium is the +4oxidation level, which accounts for the green coloration.

Organic reducing acids, such as citric and tartaric acids, dissolve sodium-vanadiumoxides very slowly, giving deep blue solutions. Oxidizing agents such as permanganate,dichromate, and persultate have little effect, either in acid or alkaline solutions.

The relatively weakly oxidizing hydrogen peroxide gives a violent reaction whichgoes to completion rapidly if the temperature is allowed to rise spontaneously, and resultsin a deep red solution. This reaction is one of the qualitative tests for vanadium. Thecoloration is said to be due to the formation of a peroxy compound with pentavalentvanadium. Once formed, this p',roxy compound catalyzes the rapid decomposition of anyunreacted hydrogen peroxide.

AREAS IN WHICH FURTHER BASIC RESEARCHWOULD BE OF ItIMEDIATE VALUE

As a result of this survey of the chemistry of fireside deposits in naval boi!ers it isapparent that there is a complete lark of factual information in certain fields of chemistrywhich have either bee'n uninvestigntd or unreported. For other subjects much of the datais incomplrtc, faulty, ur iiwrely repwr,,cfnts speculation, not necessarily based on

"10 NAVAL RESEARCH LABORATORY

experimental observation. Some of the subjects in which factual information would haveimmediate utility are discussed below.

There is a need for the determination of phase relationships in systems containingsodium and vanadium oxides in combination with other oxides. There has been somework with systems containing vanadium pentoxide and additional oxides, this work sup-posedly being applicable to the chemistry of boiler additives, but the fact remains thatvanadium pentoxide was not one of the components of the deposits taken from navalboilers. Data from phase diagrams prepared by melting mixtures of additional oxideswith the two vanadium compounds which are actually present in most boiler deposits,that is Na 2O0V 2O4 '5V• 0s and Na 2O.2V2 0,, would be uselul for predicting the physcaland chemical effects of the use of appropriate additives.

The observation was made during this investigation that very hard layers containinglarge crystals of the mixed sodium-vanadium oxides mentioned above showed no indica-tions that these crystals had grown during the cooling of a melt. There were definitesigns of ceramic bonding, however, and there are reasons to believe that crystal growthhad occurred in the solid state. It is concluded, therefore, that a detailed study of thesintering characteristics of compounds found in oil ash using the methods of the ceramistswould be extremely useful for dc-termining the conditions necessary for the formation ofboiler deposits of this type.

It is self-evident that research toward the development of cleaning processes usingthe room temperature reactions of vanadium compounds with solutions of appropriatechemicals would be aided by accurate knowledge of the actual chemical reactions involved.

These three types of research, that is, phase studies, sintering studieu, and solution-chemistry studies, are not the only areas which would have immediate utility in the searchfor an ultimate solution to the boiler-deposit problems. There is a definite possibility thatmodifications of existirr, equipment and changes in present operating procedures coulddo nwuwh to alleviate the problems, but these subjects are outside the scope of this report.

UI I'

1t

in II

M4

PART Z - SPECIAL LABORATORY METHODSUSED IN ThIESE INVESTIGATIONS

STANDARD X-RAY PATTERNS OF COMPOUNDSDETECTED IN HIGH-VANADIUM OIL ASH ANDTHEIR SIGNIFICANCES

The following x-ray powder diffraction patterns were used for the identification of thecrystalline components present In specimens of oil ash taken from naval boilers. Theproblem of identification was not always straightforward, however, because of the greatdifficulty encountered in finding standard patterns sufficiently reliable to be used for posi-tive identification of vanadium oxides. There- was the added problem, also, of identifyingcomplex mixtures of materials.

In many instances it was possible to isolate crystalline materials by means of physi-cal and chemical methods, but without changing the crystalline structures. When chemicalmeans were used for separations, care was taken to check the x-ray pattern of the originalsample for the presence-of major lines of the compounds identified in concentrated fractions.

It was possible by heating fragments of deposit in concentrated hydrochloric acid toisolate the acid-insoluble silicon dioxide known as a-cristobalite, since such silicon com-pounds are not rapidly attacked by strong acids. Likewise it was possible to concentratethe vanadium-containing fractions of a few deposits by means.of a simple water extraction,since of the three vanadium compounds encountered, only sodium metavanadate (NaVO 2 )is water soluble. Although the material going Into solution could be identified by recrystal-lization from the water, and this was done routinely, such a recrystallization did not givean indication of the nature of the soluble compounds before the water extraction. It wasfound, however, that the water-soluble fractions were also lighter than bromoform, a liquidwith a density of 2.89, and that a physical separation could be accomplished in many casesby centrifuging the pulverized samples suspended in the heavy liquid.

Vanadium Compounds (Table 2)

The compound vanadium pentoxide V 2 0, was not identified as a component of oil ashsampled during this investigation. Since the 'X-Ray Powder Data File" published by theAmerican Society for Testing Materials does not include data for the three vanadiumcompounds detected, and since the data of the literature were inconsistent, and in somecases definitely in error, the compounds were prepared from analytical reagents, weighedin the proper stoichiometric proportions, and crystallized from melts by slow cooling.In this manner Na2O'V2 i05V.0 , Na 2O.2V30 , and anhydrous NaVO8 were preparedin a crystalline form.

The compound being designated as Na3O'VaOg'5V3 Os is equivalent to the compound ofthe same formula reported by Prandt1 (5); the ONe *W of Foster (2); the /-phase in thesystems NaVO3-V,0, and Na 2SO 4-VO described by Flood (3) and Illarionov (1); the"Compound X," thought to be NaSO4.6V2 O, of Cunningham (7); and solid solutions of thegeneral formula Na.., V 0•, for which a detailed structural analysis has been preparedby Wadsley (4).

The compound designated as Na 202V2 O is equivalenit to the V-phase of Flood (3) andIlinrionov (1), found in the system Nn 1O-VsO; and Is the 'NV3 " of Foster (2). The

11


Table 2X-ray Diffraction Data for Sodium Vanadium Oxides

of High Vanadium Content (Copper K. Radiation)

NaO"Vu9 O,.5V2 0, NaO.2V O, NaVO:'

d(A)t I/1 o d(A) I/I. d(A) IA/

9.6 15 7.05 100 4.92 758.2 5 5.86 2 4.67 1007.3 100 5.03 10 3.56 655.1 10 4.78 2 3.40 554.77 20 3.90 5 3.23 100

3.87 5 3.68 1 3.11 1003.64 50 3.C4 2 2.64 45

3.49 35 3.52 10 2.43 253.40 5 3.45 2 2.27 253.22 5 3.28 5 2.23 20

3.17 5 3.23 2 2.16 753.076 95 3.16 10 1.95 503.015 5 3.12 5 1.85 252.928 20 3.025 30 1.79 502.728 2 2.806 1 1.74 55

2.53(wide) 1 2.688 1 1.64 202.378 5 2.439 2 1.57 252.268 1 2.331 10 1.50 40

2.182 40 2.276 20 1.45 401.928 1 1.974 2 1.40 55

1.916 2 1.959 21.819 5 1.833 11.809 5 1.809 11,689 I 1.770 1

1.674 5 1,26 I

1.584 1 1.654 21.543 1 1.510 51.536 51.493 2

ýG.W. Cwuw-.hhain and A. dvS. Brasunas, Corrosion IZ:389t-4, -t (19561.t- c .•pAng il anlgstron&.i

11-it"i ::;tcn ty relative to sLrongest line.

IV.-

L '


formula was chosen to indicate that two, rather than three moles of vanadium oxide arecombined with one mole of sodium oxide because a melt of the oxides in the mole ratio ofone to two gave an x-ray diagram with no spurious lines, while a melt in the ratio of oneto three contained extra lines indicating the presence of the compound Na*0-V30 4 '5V*O,.

The x-ray powder pattern of anhydrous sodium metavanadate, NaVOp, as stated byCunningham (7) includes three lines with an intensity of 1.00 (equivalent to a value of 100under the systcm in use here). Although it is improbable that this is a true ,situation, thedata are included here because it is very difficult to take this x-ray powder-pattern withoutspecial procedures, due to the extreme hvgroscopicity. This same difficulty wasencountered by Sbrum (8), who was unable to perform single-crystal structure analysisof the compound without having coated his crystals with collodion.

This instability of the anhydrous compound in contact with air would indicate that thedetection of crystalline, anhydrous sodium metavanadate in oil ash is a virtual impossi-bility; consequently, in the work reported above, the presence of sodium metavanadatewas considered to be verified if a water extraction of a melt gave an alkaline solutioncontaining water-soluble vanadium in the pentavalent condition. No crystalline sodiummetavanadate was detected, even In the form of the monohydrate.

Sodium Sulfate (Table 3)

Identification of crystalline forms of sodium sulfate is complicated by the fact thatearly investigators were not in agreement on nomenclature. The ASTM X-ray PowderData File retains the designation suggested by Kracek and Ksanda (9) although it wasnecessary to refer to the original paper in order to learn the significance of that designa-tion, which is as follows:

Sodium sulfate crystallizes from water at room temperature as the decahydrate,NaSO.4 10H 2 0, for which the ASTM index includes a card, Number 11-647, which givesvalues slightly lower than those given by Kracek and Ksanda.

The decahydrate loses its water of crystallization spontaneously on standing open tothe air, and a new, anhydrous crystalline material knowr, as *thenarditel forms. Thedata for this compound which are given on ASTM Index Card Number 5-0631 agree veryclosely with that for the same compound listed by Kracek and Ksanda.

When a specimen of thenardite prepared by drying the decahydrate is heated above220°C (428°F) a phase change occurs. The new structure is stable to at least 7000C(12920F). Although there is a spontaneous phase change at 220°C on cooling, the hightemperature modification can be ustabilizedM down to room temperature by traces ofsodium carbonate. Sodium sulfate examined by x-ray techniques at temperatures between2200 and 7000C or after stabilization is called Na2S04 (I) and metathenardite (Card Number1-0990), or o-Na2 SO,(I) (Card Number 3-0280).

Specimens of sodium sulfate which have been heated to a high temperature in theabsence of a stabilizing foreign salt, when cooled to room temperature give an x-raypattern different from the original thenardite or from that of the stabilized high-temperatureform, and this was called Na 2SO4(Il) by Kracek and Ksanda. The data on ASTM CardNumber 8-31 is that of Fischmeister (10) who made a detailed structural investigation ofthis compound.

It has been reported that calcium sulfate (CaSO4 ) stabilizes the high temperatureform of sodium sulfate, also, and that when calcium sulfate and sodium sulfate are fusedtogether complete solid solubility over a very wide range of compositions occurs, but thestructure is essentially that of sodium sulfate (1)(Il).


Table 3X-ray Diffraction Data for Sodium Sulfate (Copper K. Radiation)

NaxSO4 from a-Na#SO,(I) Na 2 SO4 (II)Efflorescence abiliz Modification from

of Na 2SO4 -1OHO Teatured Form Heated and Cooled(Thenardite) Tmperature Form Thenardite

ASTM Card 5-0631 ASTM Card 3-0280 ASTM Card 8-31

d(A) * I/t d(A) 1/1. j (,) 1 I/fIo4.66 73 4.68 30 4.74 603.84 18 3.92 100 4.47 303.178 51 3.62 60 3.91 903.075 47 2.86 90 3.76 902.783 100 2.70 90 3.48 80

2.646 48 2.35 20 2.80 1002.329 21 2.21 20 2.63 902.211 5 1.96 70 2.46 101.919 4 1.81 20 2.37 801.891 4 1.58 20 2.23 30

1.864 31 1.56 30 2.18 201.841 6 1.50 40 2.12 401.798 4 1.35 20 2.10 301.680 12 2.08 401.662 8 2.06 30

1.605 5 1.958 801.589 3 1.877 601.553 10 1.764 301.537 1 1.738 801.512 2 1.691 30

1.497 5 1.631 101.465 1 1.619 301.429 5 1.607 201.386 3 1.580 701.324 3 1.559 70

*Lattice spacing in angstroms.fLine intensity relative to strongest line.

From these facts it is concluded that the presence of thenardite is virtually animpossibility in a blifler which has just been shut down, but if an ash which containssodium sulfate is first wet and then dried, this form is a probability.

The presence of sodium sulfate crystallized in form I would indicate that the materialhas been to a high temperature while in the presence of a material such as calcium sulfate,which will stabilize this high-temperature form, and conversely, its presence in form Mimplies heating in the absence of the effects of. calcium sulfate and other stabilizers.

CZ1lOiUjm Sulfate (Table 4)

Spcial effort was required to isolate sufficient calcium sulfate from boiler depositsfor the ident it:atiion of its crystalline state. The phase which was identified was lanhydrite,P


Table 4X-ray Diffraction Data (or Calcium Sulfate

(Copper K. Radiation)

CaSO, CaSO4.2H0O(Anhydrite) (Gypsum)

ASTM Card 6-0226 ASTM Card 6-0046

d(A)* I/ 0Iot e(A) I/ Io3.87 6 7.56 1003.498 100 4.27 513.118 3 3.79 212.849 32 3.163 32.797 4 3.059 57

2.473 8 2.887 272.328 22 2.786 52.208 20 2.879 282.183 8 2.591 42.086 9 2.530 1

1.993 8 2.495 61.938 4 2.450 41.869 15 2.400 41.852 4 2.216 81.749 11 2.139 1 ,

1.748 10 2.060 101.648 14 2.073 81.594 3 1.990 41.56-I 1 4 1.953 21.52, 4 1.898 16 N

"oLwtý•" spacing in angstrom,. V.Miitý. tensity relative to the strongest

the ,!i'tdrous variety ut CaSC, which is normally insoluble in water, but which could beextracted frow Ioiler dkpos:t'. with water, presumiably because of its very small particlesize. Re.-rystallization of tht %Aatur solution& gave gypsum (CaSO,-2H5 O) even in caseswhere crystalline calhium ..u.tate mas not dclected in the original ash.

Silica (Tabloe 5)

Every sCimc n in,•o,. " c,.t-~rafd hydrochloric acid left a small residue ofSiliCa in the crysýatline torn, :.,zin a.% a-cristobalite, a-Si j.

-~~~~~~~~~~~~~~~~ ".vr pei~nds~i~"incnv~av yrclrc Tis maiteriai Can beprepared artilio iall by hcito,-.: quarts (satd) to a temperature of i260'C (23006 F) in the

wt lhxes such as st.Om su.l;Ale, or calcium sulfate. (In the presence of fluxes,s.lica i% dcterctH at rcy-m t- -.. wrat.. . a:. o-tridymltte, which gives an entirely differentx-ray diffract ion patt-rn.j

%Iron Compoumins (Tablh 61 "

Corrons,-prt.!uct iron ,\idc.s- u usually dctected 2s ma•netite (Fc302 j or as

hem:,f ite (ci- F. U ,i. A'tsu1 .' a si r n,,l form of ferric oxide known as maghem1ie

V;.-*.y

NAVAL RESEARCH LABORATORY

Table 5X-ray Diffraction Data for a-Cristobalite

(a-SiO2 ) (Copper K, Radiation)

a-SiOM

ASTM Card 11-695

4.05 1003.53 33.135 112.841 132.485 20

2.465 52.340 12.118 52.019 31.925 5

1.870 71.757 11.730 11.690 31.624 1

4--

1.612 51. C-00 31.571 11.567 11.533

3

"0Lattice spacing in angsxroms.Mine intensity relative to the strongest

line.

(fY-Fe 3O0) has been reported as a component of an oil-ash deposit (12), the presence ofthis modification is highly improoable because maghemite is converted quantitatively

into hematite on being heated above 3;ý0 C (632° F). Precision x-ray methods are requiredto distinguish between magnetite and maghemfte since both are spinels with x-ray powderpatterns which difter only in minor details. It is assumed, therefore, that .he iron spinelnormally found fi i,,rrosion products asocilat.d with oil aah is magnetite.

Crystalline ferrous and ferric sullates or their hydrates were not d.Ntected in this

study, although thI. Presence of these rompounds was implied by the presence of water-

soluble iron coni ,,unds riving a test for sultaic.

Carbon

Under ordinary cond,,t vins rarbonaceousn materials lose volli Mie gases on being heated klvý

wiith insufficient air for rmiiplete conibustion, leaving a residu? of 2morphouS carbon, which .scatters x-rayR without difrarting t,,em. pecimnen3 of *soot' taken from WrIakes, however,

I.'

gave an x-ray pattern hai ing a single very broad peak with its boundarles at half heighl !t N, Nalbout 23 and 20 dt-crees iroler radialtion.. 'Me peak, therefore, occurrcd very nearlycoincidental with the expected major dh.fraction line for graphite. and on this basis it iscoticluded that the carbonaceous material was somewhat graplhtized. _

..S. . .. L ....... 1 ... J I

..


Table 6X-ray Diffraction Data for Iron Oxides.. (Cobalt K. Radiation)

Fe3 O, w-Fe Oa(Magnetite)* (Hematite)

ASTM Card 11-614 ASTM Card 6-0502

d(A) t I/Aot d(A) I/4.

4.85 40 3.68 702.966 70 2.69 1002.530 100 2.51 802.419 10 2.20 702.096 70 2.07 10

1.712 60 1.837 701.614 85 1.691 801.483 85 1.634 101.327 20 1.596 401.279 30 1.484 70

1.451 801,348 201.309 401.255 301.224 10

tThe compound y-FeSO3 and many otherspinels give almost identical patterns.

tLattice spacing in angstroms.tLinc intenisity relative to the strongestline.

PROCEDURE FOR THE DIRECT GRAVIMETRIC ANALYSISOF HIGH PERCENTAGES OF VANADIUM IN OIL ASH

The following gravimetric method of analysis for vanadium was devised in order tofill a need which has developed; that is, for the analysis of oil ash taken from naval boilers,in which the vanadium content, calculated as the pentoxide, may be of the order of 80percent.

The basic idea for the precipitation was obtained from the work of Morette andGaudefroy (13) who reporfed that vanadium (IV) hydroxide and sodium vanadate (NaVOO)are precipitated quantitatively by sodium bicarbonate when the vanadium salts are in asolution containing 50-percent acetone. It was reasoned that if ammonium hydroxide weresubstituted in the precipitation, ammonium vanadate should be precipitated, and that this,on ignition could be converted into vanadium pentoxide and the vanadium weighed as such.Although any tetravalent vanadium precipitated would be oxidized to the higher oxidationstate on ignition, it was felt that prior oxidation with hydrogen peroxide would be desirablebecause this would place any iron present in a condition suitable for separation beforeprecipitation of the vanadium. .

The method of analysis is as follows:

A 0.3-gram portion of the sample is reduced to a powder and dissolved in 50 ml ofconcentrated 11CI while bing heated nearly to boiling. After the solution has become aclear green color, 50 nil fi water is added, and the residue (mostly s~ilica) is filtered off.


To the cool filtrate is added 10 ml of concentrated (30 percent) hydrogen peroxide, andthe mixture warmed gently until the violent effervescence subsides, and the solution hasbecome deep red in color.

To this oxidized solution is added sufficient concentrated ammonium hydroxide toneutralize the acid, and then 5 milliliters more. At this point any rust-colored precipi-tate represents the R20 3 group along with a small amount of occluded vanadium hydroxide.(In the present work it has not been found necessary to recover this vanadium.) If aprecipitate forms, the solution is filtered. The residue can be analyzed as RaOs ifdesired.

To the cooled filtrate is added an equal volume of acetone. A white turbidity appearsimmediately, and after having stood for at least twenty minutes, this can be filtered offquantitatively. This residue, which is mostly ammonium vanadate, contains someammonium chloride. It may be washed free of entrained liquid with as much as 100 mlof 85 percent acetone without rendering the vanadium soluble.

The filter paper containing the precipitated vanadium must be dried and ignited care-fully in order to prevent the expulsion of vanadium oxides along with the ammonium salts,and to prevent too great a reduction of the vanadium oxides. The residue is igrAted under

* oxidizing conditions in a weighed quartz-glass crucible at a temperature sufficiently highto melt vanadium pentoxide. This compound should be a clear, red liquid, containing nosigns of solid particles at a red heat. On cooling, the vanadium is weighed directly asvanadium pentoxide.

ANALYSIS OF HIGH PERCENTAGES OF VANADIUM INOIL ASH USING X-RAY FLUORESCENCE TECHNIQUES

Two x-ray methods were used for the rapid analysis of the vanadium content of oilash In specimens containing very high percentages of vanadium. One is based on theassumption that the intensity of secondary x-rays emitted by a specimen Is a function ofthe concentration of the particular element being assayed.

The other method is based on the fact that the secondary K/g radiation of chromiumis absorbed by vanadium in the specimen, and that this absorption is proportional to theconcentration of vanadium. This method of analysis was suggested by the fact thatchromium had not been detected in any boiler deposit and by the fact that vanadium filtersare chosen by x-ray diffractionists for the absorption of chromium K# radiation.

The Estimation of Vanadium by the Measurement ofChromium Klj Alsorpti.)n (Method 1)

A series of samples containing known quantities of sodium sulfate and vanadiumpentoxide was prepared. Exactly 0.4300 gram of each of the mixes was mixed withexactly 0.0218 gr.,in of chromium oxide under trichloroethylene and then dried.

Each of these prepared mixes was added to exactly 0.700 gram of methoxycelluloseand mixed thoroughly (while dry). Pellets were pressed in a conventional metallographicalspecimen press using one-inch dies.

With the x-ray fluorescence unit operating at 40 kv and 10 ma, and with the scaler ata time constant of 2 seconds, a scan was made over the spectrum of secondary radiationsat the rate of one degree per minute. A lithium fluoride crystal was used as a diffractiongrating.


so

60 Fig. 6 - Typical calibration curve for esti-Som ating vana dium content of oil ash by

absorption of chromium K0 radiation,40 .-

•30-

20-

toCI II

o 20 40 so so tooV2%'" STANDR IWEiNT%)

The x-ray intensities of chromium K8 radiation from each of the standard samples,when plotted as a function of the known vanadium content, gave an empirical graph (Fig. 6)for the estimation of the vanadium content of unknowns which were prepared in the samemanner.

The Direct Measurement of Vanadium SecondaryRadiation as a Means of Estimating VanadiumContent of Oil Ash (Method 2)

A calibration curve for the estimation of vanadium in oil ash was prepared fromsamples containing known amounts of vanadium and sodium sulfate, made by mixingweighed portions of pure compounds under trichloroethylene, followed, after drying, bypelletizing in methoxycellulose. The proportions of mix used were 0.4309 gram of mixedoxides wvith 0.70 gram of metho.yceilulose.

With the x-ray machine operating at 40 kv and 10 ma, and with the scaler at a timeconstant of 2 seconds, a scan was made over the secondary spectrum at the rate of twodegrees per minute. A lithium fluoride crystal was used as a diffraction grating.

When the x-ray intensity of vanadium Ka radiation was plotted as a function of vana-dium content, an empirical curve (Fig. 7) was obtained for the estimation of vanadium inunknowns prepared by the same procedure.

THE QUANTITATIVE ANALYSIS OF CRYSTALLINE Na 3 O.V2 O4.5V2O*and Na2O-2V2O5 IN THE PRESENCE OF ONE ANOTHER USINGX-RAY POWDER DIFFRACTION METHODS

The ab.1irice of N, 2O'2VO., from several oil-ash specimens which contained bothNt 2 O.V 2 0 4'5V 20*, and Na 2 SO4 In substantial percentages, but which could be partiallyconverted into this compound on being melted, pointed out the need for an estimation ofh,, linits fif detectimon of this vanadium compound in the presence of the other.

JN • -- 2.... .""'


I:Fig. 7 -Typical calibration curve for esti- 16omating v a na d i um content of an oil ash by

The two compounds were prepared by fusion of appropriaye amounts of NaVO, andV•O, (with allowances Thfor the fact that commercialobaiereagent labelledtheNaVO 5 "met wasreud '••

Factually NaVO,-H,0). Tecrystalline material obandon cooling te etswas re1e!•diffrac~toot pass throughtehiusa 200-mesh sieve and then tested for homogeneity by x-ray powder- )?/

rdifactiontehqus

Weighed portions of the two pure compounds were mulled together under trichioro-ethylene, followed by evaporation of this solvent. These standard mixes containing valriouslevels of concentration of the two compounds were pressed into a glass powder-specimenholder, and a scan made of the powder pattern. Although the most intense diffraction ,,•

i ~lines have a tendency to overlap at very high percentage compositions, the calibration \curve is empirical, and the accuracy of the analytical method is not affected by this .- •

= ~interference. •

The characteiisti. spacings which are compared in order to obtain a numericat value

which is a function of thc percentage composition of the specimens are the two most intenselines. That which was chosen to represent Na 2O-V,0'5VOs has a value of about 7.3 A,

." while that chosen to represent NaO.2V2O, has a value of about 7.0 A. Neither of theseS~lines appears in the diagram of the other compound, contrary to the data of Foster (2),

i whose compound "NaaO'3V2 05" actually is a mixture of the two.

i ~Using copper K, radiation front a Norelco tube operating at 35 1v and 18 ma, the .x-ray pattern was traced at the rate oi one-halt degree a minute over the "20" regionw••

from 1l to 13 degrees, using a tinie conmstant of 4 seconds. TPiv intensities over back- F.ground were estimated in chart divisions, and a ratio taken e1 the intensity of the line dueto Na•O.2V 2 O5 c's that due to Na 2O'V•O'5V•O,, A piot of this ratio against the percentage

Scomposition with respect to one of the conipouno• gives a curve (Fig. B)wihmay --.used for estimating the relative amounts e1 the two compounds in a mixture.

S~~~~The diffraction etficien,:y of the NaaO'2Vm•O• is so much greater than that of .,. t, ~~Na 2 O'VO 4 .5Va O• that an x-ray pattern having major lines for the two compounds of .-

equal intensity actually contains only 15 percent Na 2O.2V 3O,. A mix containing 6.7 e•,.percent Na2O.2VO• gave a onjor line intensity of 1/3 full scale, indicating that this .e"compound is detectable in quantities of the c tier of one percent.

r t .* W tNx;.: :V

so-


0

-' o f t e P a n n n

4 -

S.2--

0 0 20o 30 40 50 60 70 W 90 1N t0 0"

of two oxides of siodium and vanadiusn by an

x - ra y p o w dl e r d if f r a ct io n m e t h o d-L

..

ACKNOWLEDGMENTS

Visits to ships at the Norfolk Naval Shipyird were arranged byMr. FrankW. Edwards

EstaiaintDepartment, and assistance In collecting stag specimensfrom ships' boilers was supplied by maintenance personnel underMr.

E&G. Janson, Master -

,41

4ý

WNS.* -- 4 ;

REFERENCES

1. lllarionov, V.V., Ozerav, R.P., and Kil'disheva, E.V., Zhur. Neorg. Khim. 2:883-9(1957)

2. Foster, W.R., Leipold, M.H., and Shevlin, T.S., Corrosion 12:539t-548t (1956)

3. Flood, H., and Sbrum, H., Tidsskr. Kjemi. Bergwesen Met. 3:55-9 (1943)

4. Wadsley, A.D., Acta. Cryst. 8:695-701 (1955)

5. Prandtl, W., and Murschhauser, H., Z. anorg. Chem. 56:173-208 (1908)

6. King, B.W., and Suber, L.L., J. Am. Ceram. Soc. 38:306-11 (1955)

7. Cunningham, G.W., and Brasunas, A.deS., Corrosion 12:389t-405t (1956)

8. S~rum, H., Klg. Norske Videnskab. Selskabs. Forh. 15:39-42 (1943)

9. Kracek, F.C., and Ksanda, C.J., J. Phys. Chem. 34:1741 (1930) %

10. Fischmeister, H., Acta. Cryst. 7:776-7 (1954)

11. Bredig, M.A., J. Phys. Chem. 46:747 (1942)

12. Greenert, W.J., Corrosion 18:57t-67t; 91t-102t (1962)

13. Morette, A., and Gaudefroy, G., Compt. rend. 231:408-10 (1950)

22 '

77 7e

fl

APPENDr,• A

S.OURCES OF DATA ON SYSTEMS CONTAININGVANADIUM OXIDES

N IiI~~,..°•

K- .t '.

I~iE


1ytm Type of nsType oComnsR erencesSystems lInvestigations Data Given ___ompounds Refrece

Aluminum

A120O,-V 2 0% Additives Phase diagram, X-ray AIV0 4 Al

Al ,0 3 -VO 30 Additives Liquidus diagram via A2Seger cones

A1 2 03 -V20 3 Phase Study Phase diagram (Al,V)a 0 A3Al 2 O3 -V2 0 Ceramics research Petrographic 2AI 20 3'V2 0 A4Al 203 -V2 04 Ceramics research Petrographic Al0 'V2 s04 A4

Arsenic No pertinent references

Barium______________

BaO-V,0 5 Chemical Minimum temp for A51 reaction

DaO-V 20, Ceramics reerhPetrographic Glass A4BaO-V 2 Os Preparation ot Chemical 3MnaO2Vto A6

vanadate r

BaO-VzOa Ceramics researchi Petrographic Compound (?) A4Beryllium _________ __________ ______ ______

BeO-VU 03 Additives Liquidus diagramvia A2

BeO-Va 0 5 Ceramics resew ch Petrographic BeO*V1 q A4BeO-VAIO, Ceramicsresep-rchJ Petrographic BeOqVO?). A4

Bismuth No pertinent references _

Boron

B 1O.-Na.C%! Gas evolution hemical A7

kadmu.um No pertinent references _._

Calcium ____

CaO'V 3 0 Additives LIquldus diagram via A2

I Seg~w ConesCaO-V 2 06 Phase study Phus diagram CaOV,0 5 A0

2C a.V1. 0O. 0,3CaO.V 0,

C2O-V'2O, Chtmical MInimum temp!or ract ion

C-O-VC0O Iron-0reflahg qla Chemica None ests A9CaOV1 04 Ceranik-i retrearch Ik~roraphlc o mpxd; A4

Ca-V•~Oi2 h -reflnlng slags Chemical CaoOV 0 A9I- .cao-v..os4


Systems Type of 'Type of Compounds ReferencesInvestigations Data Given

Cerium

CeO.-V.0 5 Ceramics research Petrographic CeO2j.V2 A4

CeO2 -V2 Os Chemical Minimum temp for A51Cermicsreserchreaction{____________

CeO, -V 2 04 Ceramics research Petrographic 2CeO=._V_ O A4

Cesium

Cs; CO, -V, % Gas evolution Chemical A7

Cs, CO 3 -V2 %s Preparation of Chemical Cs 4V2 0 A6vanadates

Cs3 SO,-V, % Preparation of Chemical Cs8O-2 V208 A6vanadate s

Cs3SO4 -V2 0 5 Catalysis X-ray Cs ,SO "V0 5 A1O

CsVOQ-CsCI Phase study Thermal None All

Chromium

Cr 3 0 -V2 05 Additives Liquidus diagram A2via Seger cones

Cr 2 03 -V, 0 Crystal study X-ray data CrVO4 AI2

Crj 03 -NiO- Additives Liquidus curve A2V,0 5 via Seger cones

Cr2 03 -V2 0, X-ray study Phase diagram, (Cr, V) 003 A3X -ray _

"Cobalt

Co3 04 -V2 Os Additives Liquidus diagram A2via Seger cones

CoONV0 3 JElectrolytic X-ray COO-Va O A13

pIreparation ofs ir:,'IS j _ _ _ _ _ _ _ _

Cot p4Ž-'r

CUO-VIO,7Phna. s-tudy lX-rnv data 'CUO*V40 A14"CuO'V2 0O4CuO VO04CuO'VO5Cu;0>V2O$

CuO-V' 0' Additives LiquiduS curve A2via Seger cones

cuO-VaOl Chemical Minimum temp AS

for reactiorIron

-F:O•VC o -0,= _V PaseM y ]has di, a ,,ran - FeV O0 A15and X-ray data FeVa 04

FeO,-V2O, [Additives | Liquitdus curve A2v. . Se:er cones

p ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ : I1.._ ir 11'r.. rIJ ........ rnL... . . .... L7.7-•....

26 NAVAL RE SSA2CH LA BCOATORY

System Type of Type of Compounds ReferencesSysems Investigations DaaGvn

Iron (cont'd.)

FeO-V2 0 Preparation of X-ray data FeO.VO,, A16vanadium spinels

FeO-V 203 Studies on X-ray data FeO'V2 O, A17vanadium spinels

FeO-V2 0. Electrolytic X-ray data FeO'V, 03 A13preparation ofspinels

Fe2,% -VOs Oil ash Phase diagram FeVO 4 AI8-corrosion and x-ray data ______

Lead __ _____________________

PbO-V2 . Chemical Minimum temp I A5Lithium

LI2CO -V205 Oxygen evolution Chemical 4Li2 O.VOg. A7

K Lithu I 7_ o ea t o V 3 0 5LiCO, -VOO ,Oxygen evolution Chemical LiVO3 A19

Li 4V, 0,

Li,CO,-V,30: Preparation of Chemical L1V1A

U1.ýOiV2O, Preparation of Chemical 4L,0-5V305 Avanadate s

LiVO1 -VO Phase study Phase diagram LIVO3 A20and x-ray data UIO-3V,O,

LiVO,-LiCI Phase studt, 4Phase diagram None formed All

Mgo-v 0 Ceiamics rvs~rhPetroiraphic ýg-j$AMgO.V',O

Nhio-VAO. Additives Liquidus curve A2via Sevgr cones

M g-VoD - Oil a21h problem X-ray Unidentified A21

4IgO-V, 0. (t.'ramics research Petrographir 4MgO.VO4 A4MgO-V 3O

M•;- V.O iPrepa I.atrio ot X-ray data MgOV, G A16" Van'adium spincl$

rMgO-VAOj X-ray study tit X-ray d'0ta 4M4).V30 A1?

Mh.O-VAO. 1'hase study X-ray data %MgV, 0" A22(etc) Mgvo

...... ...

% 7


Systems J nettons aTa& of Compounds Referencesýatiun DataGivenManganese_______

MnO-V2 O, [Phase study X-ray and thermal Mn(VO,)a A23data MN V,07

Mn,(V0 4).MnO-V, 0, Preparation of X-ray data MrO.V2 0 3 A16

vanadium spinels

M11O-V 2 0 3 X-ray studies of X-ray IdnO*jV,03 A17

preparation of

___________ spnels_________

!Nickel_______________ ________ ___ __

NiO-V 205 Additives Liquidus curve A2via Seger cones

NiO-V 20 3 Chemical Minimum temp A5

___ - j _ _vla.ýegercones_-____- ~~~~~Niobium_______________________

Nb.0-V. C) Ceramics i '-t~arch Ptetrographiic Solid solution A4I I ~compound(?Nb1 -,V.101.. C#.. ramn ic s re suac Pet!rogghc____ 2 Nb2Os*V304 A4

Pbosphorus ___ ______

P. 0 -NaVO Oxygen evohiuo 10 heia A7

4-V .0ý_ J

KCo, -V..0, IPhasie studv IPhase dia~grari An.4,,and x-ray data K20-V2 0,16K,0O9V,03

iK 2 0.V,0S

Kac0, -Va0, P repratt't ol K4V, 0, A63

K~cU0 -v 0o 0nyen evoiut wIM iChemiical 2K 2 0 3 0 A71

K s L) - 0, 0+\%--ý evolution lChumical KVO, A192nd pha~sv diag~ram IK.V 2,O&

'ChcmicalCall) K2S04-V20, A25

K5 1O-V 2 0, Preparatiniu )ii ChlInical 2K,0-3V 206 6. ,

KIS .0.- V ~0 1Cataly~ss Chwt-MC21 Glass A25KV0, -K(' I ThYse %tudy Phase dlagrani No compounds .l11

j~-K r Phasc 'dudy ~ Pi "iae dingratn No cT I A%

I;.>.

28 NAVAL RESEARCH LABORATORYoptds RfrceI

Systemsj Type of Type of Compounds ReferencesSysems Investigat ions Data Given

Rare Earths

R 2•• 3-V 2 0slCrystal study X-ray data RV0 4 A26Rubidium . .. )

Rb 2 CO 3 _-V2 •5 Preparation of Chemical Rb 4 V20? A6

vanadates

Rb 2CO3 -V, Os Oxygen evolution Chemical No "bronze" A7

Rb2 SO4 -V 2 01 Catalysis X-ray data Rb2SO4 .V 2 0 5 Al0

Rb 2SO4 -V 205 Preparation of Chemical Rb2 0.2V2O, A6vanadates

RbVO,-RbCI Phase study Phase diagram No compound All

Rhodium ____

Rh20j -V•O, Crystal study X-ray data RhVO, A12

SiliconSiO, -V•0 Thermal analysis No compound A27SiO2 -V O Phase studies No compound Al ,•

sio, -V. C' Ceramnic research Petrographic SO+ 0,A4

SiO,-V0 Ceramic research Petrographic No reaction A4

SiO, -VO• Iron-retiningslaigs No reaction A9

SilverA0) Oyel tVoluion Chemical Ag92 VI0O4 A7

A5VV ~v.n vltin{ 205 L___I...... - .v o,NL

NaVO, -VV0, Phase study Phase diagran NalO,10 4 . A285VI0S

z .02V$0NaVO ,-V.0, Cr.ystal study X- ray data Na,.. VoOl, A29

N.iVO, -V 0, Crystal study X-ray data NaVO A30

Na :CO,-VOQ 0Ž.-.clr olution Chiumical Na.O'V2 O0" A\ ?-V:03

15V'O'

N.1 CO. -VO;.O ij).,lrat lon lt ('h,.,cal 2N.O-V:0S A6

Nd .CO -V.0.. Ptiast !%)(I~V t'iasis diagramn Nav0, A19I

N1 \IO -V: 0. iMa.I -tudv Phase dia.4ram Na20VV 2 AI I AU,and x-ray datlt 5V 0

\;': So, -V;O• Olq~ -I udyrbl andia•x ) :•. dt aa. O-~~ A21 ,••

-N:, .SO,-VO. Oi -:'- prvbh i .Phase diagram NaaSO4 "6VIO, A21- and x -ravdala i NaVO.

N'.S0.-:- . PrIl I: .,•, on (t Chemical 2Na O" 0 A6

N le.

NAVAL RESEARCH LARORATORY 29

SysemsType of Type of

Systems I IvsiainDtGiv~en Compounds ]Rehrences

Sodium (cont'd.)NaVO,-NaC1 I Phase study Phase diagram j No compounds All

Strontium

SrO-V,OO, Ceramics research Petrographic J Glasses A4 0*1SrO-VaO 4 Ceramicsresearch Petrographic I Compound (?) A4

SrO-V20 4_ Vanadium spinels X-ray data [BrVO 4 A22

Thallium _

Ti CO3 -V0 5 Phase study Phase diagram TIVO3 A19STI•VtOT

TIS VO_ _Titanium

TiO2 -V20 1 Ceramics research 1Petrographic 1No compounds A4TiO3 -VO 4 j Ceramics research Petrographic (TI,V)0 4 A4

Uranium _.__

U3 -V2 Os Ceramics research Petrographic 2U, On3VSOe A4

U309 -V303 Ceramics research Petrographic (U,V),O A4

Zn0-V 206 Additives Liquidus curves A2via Seger conese

ZnO-V, 0, Chemical Minimum temp A5 Mfor reaction

ZnO-V. 0 Vanadium spinels X-ray data ZnO.V0s AIM

ZnO-V20 3 Vanadium spinels X-ray data ZnOV 0 3 A17ZnO-V 0, Electrolytic X-ray data ZnOV3 O02 A13 .z

preparation ofspincls -

znO- V, 0, Spinels X-ray data Zn__V__O____ -O.-

Zirconium

zvO,-VOT Phue study hermal data C-ompoud Cable A31" aborve 730O"C

IZrO•-V O• Ceramics rswearch 1Petrographlc No reaction A4ZrO-V, 0. Vanadates Thermal and ZrV3Ov and A32

C c-ray data Zr(VO.).._Z rOa-V, OA Ceramics research __tr__•.r••c No rearction A4

"*.f,"

:0.:::

"d#.

1.4

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30

S%'•, %


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sN

! , 4

%

% 'b

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32

'. .. C- .4. ,

%


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.• %•% . F,

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35. Fo>iy, IR.T. (Chairnian), *'T1e irercn Status of the Oil Ash Corrosion Problem,* "."Corr•,.icn iilS39t-372t (195.8) ,,"

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S, . ,R•" • '•'='I •%' -N "--•%-- '_r•'• • -'•"•. '•-' -'•'-• •'•/--' •- .- '• ,-• , • .. .. .. . ... .• . ..... ..... .. .. ... . . • -- 7 '• "e


37. Friederlch, E., and Sittig, L., *Preparation and Properties of High Melting LowIOxides,' Z. anorg. u. aligem. Chem. 145:127-40 (1925)

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40. Guiter, H., "Alkali Uranates Columbates and Vanadates Prepared by a Dry Method,*Compt. rend. 209:561-2 (1939)

41. Hartmann, H., and Maessing, W., "The Electrolysis of Vanadit'rn, Niobium, andTantalum Oxides in Phosphate Melts," Z. anorg. ailgem. Chem. 266:98-104 (1951)

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45. Johnstone, H. F., and Rinsche, W.E., 'Fuoed Salt Mixtures as Reaction Media,'Ind. Eng. Chem. 36:435-9 (1944)

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Phenomena ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ W oný Ga-ubn MaeilNtHg eprtrs 'TeBonBv48. Kind, A., "Experimental Set-up for Investigating Ash Deposition and Corrosion

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49. Kiyoura, R., "Mechanism of Promotor and Carrier Action on~ the V2 05 -Na2 O-S103Catalyst,' J. Soc. Cherdi. Ind. Japan 42-:Suppl. Binding 102-3 (1939)

50. Klem-m, W., "Lower Vanadium Oxides," Z. anorg, Chem. 250.42-55 (1942)

51. Kien'mi, W., and Hoscheck, E,, "NMagnetic Properties of Some Simple VanadiumCompounds" Z. anorg. 21ilgem. Chem. Z26:359-69 (1936)

52. Lanmher1 .son, W.A., 'Fireside Deposits - A Study of Minerals Contained in FiresideDeposits of Oil-Fired Boilers," .1. Am. Sec Naval Fiig. 61:368-73 (1949)

53. Lee, V.J., and Parravano, G., "Whisker Growth on Van-adium Pentoxide Surfaces,*PB 140 548, March 1959

54. Lepinshikh, 13.M., Esin, O.A., and Manalkov, A.l., 'Electrolytic Deposition of Chro- ~ ,~mrium and Vanadium From Mielted Slags," lzvest. Akad. Nauk S.S.S.R. Otdel Tekli.Nauk. Mut. 1. Toplivo, No. 5:19-21

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-. OPIUM"


56. Logan, H.L., *Corrosion of Type 310 Stainless Steel by Synthetic Fuel Oil Ash,*Corrosion 15:443t-446t (1959)

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Carbon," Izvest. Sibir. Otcdel. Akad. Nauk S.S.S.R., No. 11:77-88 (1960) kA

65. Matveenko, 1.I., Fel'd, P. V., anI Alyanmovskii, S. I., 'Reduction Kinetics of VanadiumPentoxide by Hydrogen,' lzvest. Vyashikh Ucheb. Zavedenii, Chernaya Met. 2 (No. 4):13-21 (1959)

66. Mergault, P'., "Decomposition Voltages of Some Oxides vissolved in Molten Cryoliteat 1020'C.' Anni. phys. I 1313:179-229

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68. Milligan, W.O., Watt, L.NM.. .ind Rachford, 11.1., 2"X-Ray Diffraction Studies of HeavyMetal Orthovannr tsi J Phys. C~her. 53:227-2.14 (1949)

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71. Morette. A., arid Gauklýtroy. G., 'The -Separation and Analysis of Four-Valent Vuaiadiumand Five -Valent Vanj~tdrm,* Compt. rend!. 231:408-10 (1950)

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Natui~~~*-i 1.9.4v 110

X7V _IZ_%NN I

i-M -t L n"

36 NAVAL RESEARCH LASOP.ATORY

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NAVAL RESEARCH LMiZRATCORY 37

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38 NAVAL RESEARCH LABCRAIORY

111. Zyazev, VL., and Esin, O.A., aViscosity and Density in the Systems V3 05 -Fe.O 3,V20 5 -CuO, and V2 05 -CaO-Fes 0 3, Izvest. Sibir. Otdel. Akad. Nauk S.S.S.R.,No 10:13-20 (1958)

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