AD-AI42 425 TRACE ANALYSIS IN OUARTZIUI EAKE PIChE IStUIs INC I/ fMIAMI ORl A 64U11.* dACi -51.S

UNLSIIDF19W20s1-C-0072 F/0 7/4 NL

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A ONAL DUPE AO OF STAND 'RDS- 1963-.

1i11 I .

RADC-TR-84-51Final Technical ReportMarch 1964

TRACE ANALYSIS IN GUARTZ

Eagle-Picher Industries, Inc.

'¢ A. L. Fluemneler

AM OVE FOR FU , a4W 81MBmOOK H/#/.I/E'

IDTICELECTEROVE AOR DEVELOPMENT CENTER DIO t4L2MI198

Air Force Systems CommandGrlfflss Air Force BS", NY 13441 E

84 06 26 005

i-ii-I I IJ

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RADC-TR-84-51 has been reviewed and is approved for publication.

APPROVED: (5

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0 &AM OP PIPOAMING ORGAfIZATION OPPICS sVuoL 7,U NAM OP MONITORING ORGANIZATIONEa81e-ichert~c. (It fEagle-Picher Idustries, Inc, Rom Air Development Center (ESME)S ecialty Metals Division

E.. AOIeSs (cit. Sam M Zw Code) 7u AOCIs (Cit,. sMe -- ZIP Cadet

P.O. Box 1090 Hanscom A€F MA 01731Miami OK 74354

ft NAME OP PUN0INGJ "ONSOING a. OPPIcs sYMUOL IL PROCUNI9MNT INSTRUMENT IOINTIPICATION N'UMEER

ORGNIZAION fit PUI

Rome Air Development Center ESME F19628-81-C-0072

OL AOONIS (CIly. SmaM Md ZIP CP) 14. SOUnce OP PUNOINO NOS.

Hanscom AFB MA 01731 PROGRAM PROECT. TAS WORK UNITELEIMENT NO. No No. NO.

62702F 4600 17 49

TRACE ANALYSIS r. QUARTZ

1Z. PORSONAL AUT"ONIS)A. L. Fluesmeier

13a Type OP NEPONT 1:111 Time COVEtsO 14. OATS OP NESPORT (Yr.. Me.. DaysI IL PAG$ COUNT

Final I PM Jul 81 ato Dec 831 %trch 1984 24I. SJW tLMEN1ARY NOTATION

N/A

PIEL GROUP I 8uAn. Quartz Crystals07 02 EPChemical Analysis

1.AWYNACT lCowaow - Mftif Wwar ai 1*J, y =

- he objective of this work was to devise a technique capable of determining trace impurities

in quartz at the parts per million range. The technique selected was atomic absorption and

a procedure was devised for determining lithium, sodium, potassium, iron, aluminum and

carbon. Over 150 quartz samples vre analyzed using this technique.

L OISTMrIETIO WAVASLA8 I1TY OP AETIACT 21. ASSTRACT SECURITY CLASEIPICATION

UNCI.AMPIOSIUNMITIG (AM $AS ̂NP". C ovic ysams (3 UNCWASIFIED

RAf MA OP AS ISOU INGIVIOWOA, Ef TILJP Of E NUMUER 22.. OPPI CE sYMOcI.I hoi Ala COO#a

Alton 7. Armington (617) 861-4834 R.ADC (ESME)

00 FORM 1473,83 APR es1tieu 0O 1 IAN 73154 OsEOLi U.CLASSIYIEDsCUNiTYv CI.AS5IPICATION OP T"Is Pa.-oF

TABLE OF CONTENTS

Page

SECTION I - LITERATURE SURVEY ...... ................... I

SECTION II - ANALYSIS OF SAMPLES ......... ............... 2

APPENDIX I ........... ............................. .. 14

_Aees ion For

NTTS G4P&IDi, T -

U' -

J.. -' ' ' l !I I

This final report covers the work performed on Department of the Air

Force Contract No. F19628-81-C-0072 by the Analytical Department of

Eagle-Picher Industries Inc.,Miami, Oklahoma and covers a period of time

from July 1, 1981 through December 31, 1983.

I LITERATURE SURVEY

The first part of this contract was the performance of a litereture

survey of analytical methods for trace analysis in quartz and fluoride

glasses.

During this search the Dialog on-line retrieval service was used. This

service allows many sources to be checked in a relatively short time.

The literature for the period 1972-1981 inclusive dealing with quartz

and fluoride glasses was surveyed using the Chemical Abstracts data base.

Key words which were used in the broadly defined search were the followirc:

quartz, impurity, silica, lithium, sodium, potassium, aluminum, fluoride,

fluoride glass, analysis, determination and amorphous. A total of more than

2100 articles were identified about 10% of which were pertinent to the

project. It is not surprising that most of the analytical references fourd

were for impurity levels much higher than we were interested in. 4t

therefore became necessary to develop an analytical procedure suitable tc

our purposes. The results of the literature search were forwarded to the

1

contract monitor. The analytical procedure developed in this laboratory was

used for subsequent analytical work on this contract. A copy of this

procedure can be found in Appendix I.

II ANALYSIS OF SAMPLES

A total of 205 samples were analyzed on this contract. These included

not only samples of quartz and quartz-growth related materials but also

samples of Lithium Niobate, Indium, Phosphorous and Indium Phosphide.

Almost all of the samples were analyzed using the analytical procedure

developed in this laboratory. (See Appendix I) Some of the SDecial

samples, however, were analyzed by Emission Spectrogrpahy using a standard

laboratory procedure.

The analytical procedure developed in this laboratory proved to be very

good in that it allowed very little opportunity for sample contamination.

The limiting factor in this procedure is not the dissolution of the sample

but the final detection of the required elements. Atomic absorption was

used during this contract. This limited our detection limits due to sample

dilution. We intend to use an Inductively Coupled Plasma/Mass Spectrometer

on these and similiar samples in the future. lie expect this rew

state-of-the-art instrument to lower our detection limits for these elenentq

to the parts-per-billion range.

Analytical results on all of these samples are reported in Tebles T

through Tables VII.

2

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TABLE IlAf Contract F-19628-81-C-0072

LITHIUM N1IOBATE

lg /g

Ident. Si fig Fe N i AlI

LfIB-l 235. 8. 1360. 320. >2000.3Lri-6 102. >1000. 1190. 275. >2000.UCN-2-4 64. 4. 1030. 230. >2000.

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TABLE VI

Indium Phosphide Samples

Sample Fe Ge Sn8-29-83

1 ND ND 35.2 ND ND 53.3 ND ND 63.4 ND ND 50.5 ND MD 61.6 ND ND 76.7 ND ND 640.8 ND ND 7800.A ND 2500. NDB ND 2000. NDC ND 126. NDD 580. 50. ND

9-20-83Special (Ahern) 2.8

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13

Appendix I

Analysis of Quartz for Impurities

Application: This method is applicable to the determination ofaluminum, iron, sodium, lithium, potassium and silver. Two grams ofsample are required for duplicate analyses.

Summary: A sample is dissolved in teflon in a Parr bomb usingultra..pure HF" acid. The silica in the sample is then volatilized inplatinum. The impurity containing residue is put into solution usingultra-pure HNO 3 acid. The analysis is completed using AtomicAbsorption.

Apparatus:1. Perkin-Elmer 5000 AA with graphite furnace capability.2. Parr 4745 acid digestion bomb.3. Platinum crucibles.4. Volumetric flasks-l0 ml.5. Furnace or oven capable of 130 C.

Reagents and Standards:1. Ultra-pure HF acid.2. Ultra-pure HN0 3 acid,3. Ultra-pure H2S04 acid.4. Ultra-pure acetone.5. Demineralized water.6. AA standards for the desired elements.

Analysis:

1. The quartz ingot is washed well with acetone and water toremove any sealing wax used in sawing.

2. The ingot is then wrapped in several layers of kleenex andbroken into shards with a hammer.

3. The shards are then collected in a cleaned pyrex beaker andwashed repeatedly with acetone, FCI, HNOa and demineralizedwater. They are finally washed with several changes ofdemineralized water. The shards are then dried carefully.

4. A sample is weighed from these cleaned and dried shards andplaced in a similarily cleaned teflon cup for the Parr 47d5acid diaestion bomb. The shards should be small.

5. Five ml. (for a 1 gm sample) of ultra-pure HF is added to theteflon cup and the bomb is carefully assembled.

14

6. The bomb is then placed in an oven and heated at 130 C.overnight.. This should completely dissolve the sample butadditional time may be needed if the shards are very !a ge.

7. The bomb is then removed from the oven and allowed to cool.

8. The bomb is then carefully opened (wear rubber gloves andsafety glasses) and the teflon cup removed. The cup is openedcarefully to avoid spilling the contents and washed carefullyinto a clean platinum crucible.

9. Add 2 drops of ultra-pure H2SO4 and carefully heat thecrucible to evaporate the HF and thus volatilized the silicaas silicon tetrafluoride.

10. The residue remaining in the crucible (containing the impurityelements) is put back into solution by adding 3 drops ofultra-pure HNO 3 and a small amount of demineralized water.Heat gently but do not evaporate.

11. The contents of the crucible are very carefully transferred toa cleaned 10 ml volumetric flask and made to volume withdemineralized water.

12. The analysis is completed using Atomic Absorption and thegraphite furnace if necessary. Use carefully preparedstandards and blanks.

Note: All glassware must be carefully cleaned before use.Do not get anything from the outside of the cruciblesin the solution. Use rubber or plastic gloves andeye shields when handling HF and other acids.

15

MISSIONOf

Rome Air Developmet CenterRAVC ptax6 anid exWcut" &G6waA, deveopoott, tea~t ad6e.eaed quL~Wn potam 'iA 6%Wtot 06 Cou'mand, Conttot

COMMZa~t ~dInitLeiit (C21) Wac..t"~. Tedchn4Waiid neeAwLng AUppo-tt wiitkin axe" 6 otWc~icAn&L coumptmeni6 pWmided to ESP Pko~tOiujgt (p04) 4M, ockeA ESPetCuatA. rke ptbiw tekn&A ni 4.ion ea 4&eC0"WIA&Wd&QR6, ttCdt.ouszgntij gwidt and Contkot, 4(L&-veUatwe 06 g4wd and awaa ac objeet, initetgewie dataaotction and hadng, injOAatOn jAyeM tedwnotogypionoAPke~C p'Wpagaio, 4otid 4tdtt 4e-tncu, .ie~W=IVePhy4i.ZU and etmf.twku &-teU-tabV,14v W&&tintnbiU4t OAd