RDTR NO. 1691 JUNE 1970

LIS

THE EFFECT OF CONTAMINANTS

ON THE

MAGNESIUM-SODIUM NITRATE SYSTEM

D DDC

Reproduced by theo

Infofmition SrnfedVa. 22151 JJL iij7

PREPARED BY

RESEARCH AND DEVELOPMENT DEPARTMENT

NAVAL AMMUNITION DEPOT, CRANE, INDIANA

• ' €. - I''.'

PAVPI SUJITI(S DEPOTCtame. Irdlana 47522

RDTR No. 1691 June 1970

THE EFFECT OF CONTAMINANTS ON THEMAGNESIUM-SODIM NITRATE SYSTFJi

By

W!LLIAM T. BIGGSReseirch Chemist

This report was reviewed for adequacy and technical accuracy by

CHARLES A. LIPSCOMB -Physicist

Approved by

S. M. FASIGDirector, Research and Development Department

TABLE OF CONTENTSPage

Abstract ....... ...........................

I. Background ....... ....................... 1

11. Introduction ........ ...................... 2

III. Experimental Procedure ................. 2A. Doping of Sodium NitrattB. CandlesC. Spectral EquipmentD. Photometric Equipment

IV. Discussion of Results ........ ........... 3A. Relative Candlepower and Burning TimeB. Spectral Distribution

V. Conclusions ................. .... 4

References ............................ 6

TABLE I -Cation Dopant ..................... 7

TABLE II - Anion Dopant ...... ................... 8

TABLE III - Cation-Anion Dopant ................ . 9

FIGURE I . . . . . . . . . . . . . . . . . . . . . . . . . .. 10

FIGURE II ......... ......................... 11

RDTR No. 169

ABSTRACT

Sodium nitrate was "doped" with 74 contaminants. The "doped"

sodium nitrate was then used to prepare miniature magnesium-sodium

nitrate candles. Data was obtained on burning time, relative

candlepower output and spectral distribution of the energy radiated

over the region from 200 m. to 780 mft. Evaluation of the data

indicates that some dopants have advantageous effects upon the

magnesium-sodium nitrate system.

ii

M-R.0 169

Chemicals used in the pro&;ction of Silitariy iret*CInics ax-e

usually purchased under existing aili-ary specficati-rs. It is the

geneTal trnd cf caese specifitations to ipell ct average partic1e

size ad purity of the raw waterials as t eost imrt aes. r

of that rterial.

As vany experit-nceo py-otechnicians knMI, a =tqial nay weet

the required specification but fail to peron corretly. This

know' eg has led the scientist to dwell deeper ard . into

the properties of materials an-- their effe-t in a solid-sol id

reaction.

This study is part of a continuing effort to investigate an

detemine the prcperties of rap mteriais which control their

behavior in a solid-solid reaction. There coud be two aproaches

to this problem. One being a straight analytical ap?roah in iiich

all the possibly known properties of the naterial could be correlated

to the perfomance, or contaminants cmi id be added to raw vateriai

and deviatios in performance analyzed. Since lattice defects are

one of the major rate controlling properties oF a material, the

latter approach was used.I The ef-ert of contaminants on hygroscopicity

and thermnal decoiposition of srdium nitra'e has already been

reported. 2,3

S5di- aint was *&rd with 74 cowtaewnants. T-ile only

selectio, criteria ied ws tV at the dopant saterial 'e soluble s

A4qrersible in -ater. The depa,.ts mn be placed fiwtz Vtr,

Caters: cr.303, ani, and ca:-oo-Mn-t;ion.

11w dapasts could have been incorporated irito the sodi ur nritrate

Lattice as interstitial cations or catic vacancies; as interstitial

a ms or anion vacawcies; or a ixtuire of both.

111. EXPOUPMAL POCOED1

A. 00oping' of Sodium Nitrate

Sodim nitrate was dissolved in distilled water in the

proportion of 180 grains of sodium nitrate to 100 ml of water.

The contwi, u nterial was dissolved or dispetsed in a minimum

snt of distilled water and added to the sodium nitrate solution.

Tre solution was tJen subjected to a water bath at OOC for 10

minutes and the sodius nitrate crystals collected and dried.

UTh depant concentration added was five percent by weight of the

sodium nitrate.

8. Candles

Two small experimental cardles fri each of the contaminated

samples of sodium nitrate were prepared using the following

for1 lation:

Gram 16 atcnized magnesium 57.0%Doped sodium nitrate 38.0%Binder (Laminac-Lupersol) 5.0%

The candies were pressed in three 30 gram increments at

7,500 psi.

RDTR No. 169 Y

C. Spectral Equipment

A Perkin-Elmer 108 scanning spectrometer was set approxi-

mately 29 inches frri the burning candles, ar-i the output recorded

on magnetic tape. Spectrograph A was a Baus:h and Lomb spectrograph

leaded with fPus Pan-X film. Spectrograph A was set approximately

?8 inches from the burning candles, and the exposure time was 10

seconds. Spectrograph B was also a Bausch and Lomb spectrograph

loaded with HSIR film. Spectrograph B was set approximately 32

inches from the burning candles, and the exposure time was 5 seconds.

D. Photometric Equipment

Photocells were placed at four equal intervals around the

burnir:g candle, and they were hooked up to an clectronic integrator

which displays relative integrated numbers.

IV. DISCUSSION OF RESULTS

A. Relative Candlepower

Tables 1, 2, and 3 show the average burning time and

average relative candlepower for the cation, anion, and cation-anion

dopants, respectively. In most cases, the addition of a dopant

decreased the burning time and the relative candlepower. The

average bu-ning time for a control candle Wds 13 seconds, and the

average relative candlepower was 6.58. However, in Table 1, magnesium

nitrate, thorium nitrate, iron nitrate, dysprosium, and yttrium

nitrate exhibited relative candlepower which was higher than the

control candles with approximately the same burning time.

3

Jr

RDTR No. 169

4

In Table 2, the anion dopants, sodium peroxide, sodium

sulfite, and sodium borate exhibited higher relative candlepower;

and in the case of peroxide and borate, the burning time was longer.

For cation-anion dopants, boric acid and stannic chloride

exhibited higher relative candlepower and no decrease in burning

time.

B. Spectral Distribution

Figure I shows the spectral distribution in the visible

region from 380 mp to 780 mA for a control candle and dopant

candles aluminum nitrate, sodium peroxide, and cadmium nitrate.

The major difference inthe distribution occurs in the 530 to 630

mp region.

The other dopant candles exhibited no noticeable difference

in visible distribution.

In the region from 200 to 400 m. there was no noticeable

difference between the dopant candles and control candles. A

typical distribution in this region is shown in Figure 2.

No meaningful data was obtained from the film exposed on

Spectrograph A or B.

V. CONCLUSIONS AND FUTURE PLANS

Some dopant materials appeared to enhance the magnesium-

sodium nitrate systen. A new supply of doped sodium nitrate is

being prepared for further study. The dopants to be studied further

are those mentioned in the discussion of results.

4

RM. Y4. 169

A helium neon laser, will be utilized to line-up ti'e spectral

equipment for the next set of experiments, since some of the

monochromatic data may be questionable due u, possible iwT-ver

aligment.

A different formulation will be used to obtain data which wi1

be more applicable to the four inch diameter candles new used in

producti on.

5

RDR o. 169

RUElRECES

1. Garner, Willia E, Coit7of the solid Suate, &ttenr-thsScientific Pa!,icatiofls, London, Ergland, 1955.

2. Riplei, illiam, zhe effect of segeacd Conta'tw-.ts on Ow~ac-osopcit of &,di A- itmte, RDIR No. 140, 7 March 19.

3. Ripley, Villim, Diffel0?t4=1 2Tkezmal Awlyjsis Thermoo-jrm of55;.w Sitrzte Dopd ith Solecte Cont~imrats3 RDTR No. 143,12 Play 1970.

6

RDTR No. 169

TABLE I

CATION DOPANT

Average

Average RelativeDopant Burning Time Candlepower

Magnesium Nitrate 13.5 7.23Barium Nitrate 11 5.63Lead Nitrate 11 5.81Ammonium Nitrate 11 6.12Silver Nitrate 11 4.58Lithium Nitrate 10 5.47Zinc Nitrate 11 6.39Mercury Nitrate 11 5.78Nickel Nitrate 11.5 6.79Thorium Nitrate 12.5 7.21Manganese Nitrate 10 4.90Cerium Nitrate 12 6.32Chromium Nitrate 12 6.05Cobalt Nitrate 1 10.5 5.31Aluminum Nitrate 13 6.45Iron Nitrate 14 7.56Bismuth Nitrate 11 5.53Cadmium Nitrate 11 5.74Uranyl Nitrate 12.5 6.31Iron(ic) Nitrate 12 6.01Rubidium Nitrate 10.5 5.43Indium Nitrate 11 5.60Dysprosium Nitrate 12 7.06Samarium Nitrate 12 6.33Gallium Nitrate 10.5 5.89

Scandium Nitrate 11 5.82Rhodium Nitrate 10 5.18Gadolinium Nitrate 11.5 5.86Yttrium Nitrate 14 7.34

7

RDTR No. 169

TABLE II

ANION DOPANT

AverageAverage Relative

Dopant Burning Time Candlepower

Sodium Carbonate 11 5.27" Peroxide 17 7.57

" Iodide 11 6.56Acetate 12 6.64

" Fluoride 12 6.78Oxalate 12 6.16Phosphate 13 6.76

" Sulfite 13.5 7.32" Bromide 11.5 6.11

Thiosulfate 11 5.74" Nitrite 11 5.33

" Sulfate 11 5.65" Borate 19 8.31

Perchlorate 12 6.51

" Chloride 10.5 5.37

" Chlorate 11.5 6.08Dichromate 12 6.31

" Chromate 10 5.89Iodate 10.5 5.29Thiocyanate 10.5 5.57Permanganate 12 5.54Formate 13 6.98Hypochlorite 10.5 5.89

" Sulfide 13 6.62

8

RDTR No. 169

TABLE III

CATION-ANION DOPANT

AverageAverage Relative

Dopant Burning Time Candlepower

Antimony Trichloride 11 5.75

Arsenic Trioxide 11 5.92

Urany! Acetate 11 5.65

Antimony Trichloride 13 6.59Ruther'um Tetraoxide 11 5.58

Boric Acid 12.5 7.00Silica 10.5 5.94

Rhenium Trichloride 10 5.65Selenium Dioxide 12 6.02Germanium Dilodide 11 5.41Zirconium Sulfate 8.5 4.95Osmium TrichIoride 10.5 4.46Erbium Sulfate 12.5 6.59Vanadium Tribromide 13.5 6.17Stannic Chloride 14.5 8.02Gold Chloride 9 5.19Iridium Triodide 10 5.91Praseodymium Sulfate 10 5.10Tungsten Hexachloride 11.5 5.38Sodium Meta Perisdate 13 6.93Platinum Chloride 12 6.46

9

LLIa a I

A583N3 AM~3N3

LUU

Ln 0Ln

A98I3N3 9JN

_________

II I4

$S

&

w0

w c~J6~*U-

p p p p

A9~J3N3

UNCAS5JfiED - -

DOCUMENT-CONTROL DATA .R & D." t ... e .fid . h.. , rr , a.I. ..nj' .. w,... ..g. .,.," a # I., e .q t d %hen the u wtll rp ot i. riaa'4 fied)

I; ' I Itd A C I I, IT- nttptq,ce w ) 25. RCEPORT SECURITY CLASIFMcA JION

-Research and Develboent-Departmefit UNCLASSIFIED-Naval _wrnition kpot 3b. G-o Ip-Crae, I-Iiana-

ifi Jn i'lu. Soiu itat yse

The-Effect of-Conte mhants on the Ma-gesi-Sodium Nitrate system

.6 Ot, CRIP ISJ N t ES0 C71'p' 1-1 wg.,t end irpri,.js" 4d14 J

AV INOr frS irst ,iamnn, middl instial. laxt n.me)

William T. Biggs

A REPORT DA I 7a. TOTAL 40. OF PAGES 7b. NO. Or REFS

I ,iun 1970 II _ 1_ _ _ _6.8. CONTRACT OR GrART NO. In., ORIGINATOWS REPORT NUMHCRISI

h. PROjECT NO RDTR No. 169

I' .qh OTHER REPORT uOIS) (AIv oth't IJumbets that may be oanlgnedthis mr.ott)

d.

80 DISTRIOUTION STATEMENT

Unlimited

11 %UPPLM4*,N TARY Nors i: SPONSORIF.G WILII AkY ACTIVITY

13 ABI RSACT

-'Sodium nitrate was "doped" with 75 contaminants. The "doped" sodium nitratewas then used to prepare miniature magnesium-sodium nitrate candles. Data wasobtained on burning time, relative candlepower output and spectral distributionof the energy radiated over the region from 200 m to 780.mo. Evaluation of thedata indicates that some dopants have advantageous effects upon the magnesium-sodium nitrate system.

D ORM 1473 r ,D D .ac 17 UNCLASSIFIEDS -4 0 I 1. 807 ',,80I ±Ts'brvUfV Chi%? hicotlon

;- u,RutI (la -if ira Iton

•O 1- tA L IK It LINK; 1A OLt C ROLE W HOLE WT

Sodi um NitrateDopingMagnesiumSpectral DistributionBurning Timne

D D,.. 1473 (BACK) UNCLASSIFIED(PAGE 2) St' urity Classificution