NBS TECHNICAL NOTE 751

**

m

Studies of Calibration Standards

Used in the Department of Defense

Equipment Oil Analysis Program

Studies of Calibration Standards

Used in the Department of Defense

Equipment Oil Analysis Program

D. W. Golightly and J. L. Weber

Analytical Chemistry Division

Institute for Materials Research

National Bureau of Standards

Washington, D.C. 20234

NBS Technical Notes are designed to supplement the Bureau's regular publications program. They provide a means for making available scientific data that are of

transient or limited interest. Technical Notes may be

listed or referred to in the open literature.

\

a^m.

s^>*u of

U.S. DEPARTMENT OF COMMERCE, Peter G. Peterson, Secretary

NATIONAL BUREAU OF STANDARDS, Lawrence M. Kushner, Acting Director,

Issued January 1973
National Bureau of Standards Technical Note 751

Nat. Bur. Stand. (U.S.), Tech. Note 751, 48 pages (Jan. 1973) CODEN: NBTNAE

For sale by the Superintendent of Documents, U.S. Government Printing Office, Washington, D.C. 20402.

Price $ .75 domestic postpaid or $ ,50 G.P.O. Bookstore.
STUDIES OF CALIBRATION STANDARDS USED IN THE DEPARTMENT

OF DEFENSE EQUIPMENT OIL ANALYSIS PROGRAM

Danold W. Golightly and

Joseph L. Weber, Jr.

Analytical Chemistry Division

Institute for Materials Research

National Bureau of Standards

Washington, D. C. 20234

At the request of the Naval System Air

Command, Department of the Navy, studies have

been conducted on organo-metallic calibration

standards and diluent oil used in the Department of Defense Equipment Oil Analysis Program.

Consultation on standards has been provided,

and measurements of physical properties of base

oil, concentrations of major elements in

standards, concentrations of trace contaminants,

and stability of solutions have been performed.

Results of studies accomplished in fiscal year

1972 are detailed in this report.

Key words: Calibration standards; concentration validity

flash point; lubricating oil; pour point, spectrometric

analysis; stability; trace elements; viscosity.

1. INTRODUCTION

The principal objectives of National Bureau of Standards

(NBS) studies for the Department of Defense Equipment Oil

Analysis Program (DOD EOAP) in fiscal year 1972 were directed

toward determinations of physical properties and concentration validities of base oil concentrates. Priority subjects

for study were established in a meeting with Navy (DOD EOAP)

representatives on February 24, 1972 at Pensacola, Florida.

These subjects were:
1. Investigation of the concentration validity of metal

concentrates provided by supplier.

2. Characterization of paraffinic hydrocarbon base

oil (diluent) in terms of viscosity, flash point,

pour point, and trace element content.

3. Investigation of dilution accuracy attainable by

Pensacola Navy Air Base Laboratory (PNABL)

.

4. Characterization of stability of diluted solutions

of standards.

The results pertinent to these objectives obtained

through the end of fiscal year 1972, and findings on all

related studies are detailed and analyzed in this report.

Results from the long-term stability study will be supplied

at a later date, when the study will have been completed.

2. MEASUREMENTS, RESULTS AND DISCUSSION

A. Concentration Validity of Oil-Base Metal Concentrates

Eleven oil-base concentrates have been analyzed

chemically for metal content. The analysis results have

been compared with nominal concentrations from the supplier*

to ascertain the validity of the metal concentrates.

Liquid oil-base concentrates are received by the

Pensacola Navy Air Base Spectrometric Oil Analysis Laboratory

(PNABL) as single-element standards that can be blended and

diluted to concentrations suited to calibration of optical

emission and atomic absorption spectrometers. Each concentrate consists of one metallo-organic compound (an alkylaryl sulfonate) in oil**. Representative portions of 12

on-hand concentrates were received by NBS for chemical

analysis. Sodium was later deleted from the list of

35 Supplier is Continental Oil Company.

** Exact identity of metallo-organics is proprietary

information of supplier.
priority elements for DOD EOAP , and replaced by molybdenum.

No molybdenum concentrate was received from PNABL in fiscal

year 1972.

All analyses, performed by R. Bell of NBS, consisted

of classical gravimetric and titrimetric methods. Summaries

of these analyses and analytical methods are provided in

Tables 1 and 2. (See Appendix A for all tables in this

report .)

Results for all eleven elements verify the nominal

concentrations and indirectly verify the analytical

methodology used by the supplier. Agreement between supplier

and NBS values is considered to be attained only in the

instances where the mean NBS value falls within the 2 percent

relative inaccuracy range set by the supplier on nominal

concentrations

.

B. Characterization of 245-Type Base Oil

The base oil* has been characterized in terms of physical properties and trace element content. Kinematic viscosity, flash point, and pour point were determined by a cooperating laboratory. Such measurements presently are

not being made on a regular basis within the NBS laboratory.

Concentrations of 20 key elements were determined by a DC

arc-spectrographic technique in the NBS spectrochemistry

laboratory.

Results for triplicate determinations of kinematic

viscosity, flash point, and pour point are summarized in

Table 3. Results from a single DC arc-spectrographic

analysis of oxide residue on Ga~0„ carrier are presented

in Table 4. Further data are forthcoming to supplement

the results from spectrographic arc analysis.

Continental Oil Company, Type 245.
C. Dilution Error and Stability Study * X-ray fluorescence spectrometry (XRF) affords a means

for long-term stability studies and for estimation of

possible dilution errors generated in preparation of series

of diluted solutions from blended concentrates. The basic

response function for calibration, that is, concentration

versus relative intensity (counts per second, with a scintillation detector), is linear. Precision for intensity

measurements by XRF (for 100 second signal accumulation

intervals) was found to be generally better than that

demonstrated by spark optical emission spectrometry (for

30 second signal accumulation intervals) for nickel, iron,

chromium, and titanium.

Thus, present stability studies (selected samplings

from 12 different batches from Pensacola) are being conducted

by XRF on Fe , Ni , Cr, and Ti, only. Data will be collected

at intervals of 2-3 months to ascertain long-term stability.

Sufficient time to complete this study has not elapsed.

Calibration curves for these four mentioned elements

are illustrated in Figures 1 through 4. (See Appendix B for

all figures in this report.) Solid NBS Standard Reference

Material (SRM) alloys have been used to provide reference

signals. Thus, for example, the relative intensities of Cr,

K-alpha emission from oil-base standards have been ratioed

to the relative intensity of Cr, K-alpha emission from NBS

SRM 1167, which is a low alloy steel. Because Cr is homogeneously distributed in the SRM and long-term stability of

the SRM is certain, this alloy serves as a means to consistently reproduce experimental measurement conditions with

minimal uncertainty.

Experimental design and preliminary experiments were made

possible through the advice and assistance of S. D.

Rasberry.
Close observation of the curves in Figures 1 through

4 reveals that the relative intensity ratios do not adhere

to strict linearity over the entire concentration range

observed. This apparent nonlinearity likely can be

attributed to a consistent 10% dilution error made at PNABL

for the nominal 300 ppm solution. However, to a first visual

approximation, these curves are linear to 50 ppm. This

linearity provides a means for estimation of maximum

expected errors attributable to dilution. Such a dilution

error estimate is possible through first, establishment of a simple linear regression equation for the curve and second,

estimation of the deviation of points from the curve along

the concentration axis. The equation for the model curve is

Ob + b^R+E, where C is concentration in ppm, R is the

relative intensity ratio, b

Q

is the intercept on the concentration axis, b, is the slope of the line, and E is the

deviation from the curve. Deviations from five -point

(includes zero) curves are illustrated in Table 5. These

deviations are presented as relative values in Table 6.

The trend in relative error progresses as one would

expect; that is, relative error increases as concentration

decreases. Such a trend reflects the uncertainty in measurement of analytical signals as the signal magnitude decreases.

The relative deviations in Table 6 should be considered

maximal deviations because effects on the slope of the

regression curve attributable to normally distributed experimental errors have not been given account in this treatment.

However, a conclusion that there are no gross dilution

errors is appropriate from these data.

D. Other Observations on Standards

Several series of tests, principally on precision, were

performed on the MIL-SPEC spectrometer located at Andrews

Air Force Base. Twelve-element standards (designated

Batch 5/12/71 by Pensacola Navy Laboratory) at nominal con-
centrations of 0, 3, 10, 30, 50, 100, and 300 ppm, by weight,

were used in these studies. Spectrometer standardization

was ascertained with 100 ppm 12-element standard (Batch 49,

Mar. 31, 72) by Mr. Hare, Sgt. Foust, and Sgt. Speciale of

Andrews Air Force Base. Standardization of the instrument

was performed immediately before the start of each precision

study.

1. MIL- SPEC Requirements on Precision

Analysis of the data collected in the reproducibility

study on the MIL-SPEC spectrometer at Andrews Air Force

Base (Table 7) indicates a general conformity to latest

MIL-SPEC requirements (revised) on maximum deviations of

readings. The analysis of data presented in Table 8 represents results from fifteen replications, with no data drops.

2. Analytical Response Functions

Analytical response functions for 12 elements are

presented in Figure 5 through 8. In terms of the MIL-SPEC

spectrometer, these curves are plots of concentration versus

analog readout. Analog readout refers to the ratio of

voltages produced on capacitors that accumulate charge

during the interval for integration of photocurrent signals.

An ideal curve exhibits linearity over the entire concentration range of interest and, in addition, passes through

the 1-1 origin-point on a log-log plot. The curves for

several elements (Ni , Pb , Si, Ti , Fe , and likely Sn) approach

these linearity and intercept criteria. Change in slope

with increasing concentration indicates line broadening and

self absorption in the spark source. The net result of

decrease in slope is loss of precision with increasing concentration. The slope is loss of precision with increasing

concentration. The slopes of these curves correlate well

with the data analysis of Table 7.
3. Coefficients of Variation for Organo-Metallic

Standard Compared with those for Used-Oil Samples

The percent coefficient of variation provides a base100 scale for comparison of relative standard deviations.

This coefficient is defined as the ratio of standard deviation to the mean, times 100.

Occasionally, the question arises whether the precision

of measurement afforded by synthetic standards is significantly different from that incurred with used-oil samples.

A limited amount of data (Table 8) addressed to this

question was obtained on the MIL-SPEC spectrometer at

Andrews Air Force Base. These data, for six elements at

similar concentrations, are presented in Table 9.

These limited observations indicate that measurement

reproducibility for standards is essentially the same as

that for used oil samples from jet and reciprocating engines,

4

.

Spectrometer Readout for 12 -Element Blends versus

Readout for 20-Element Blends

Data were collected on the MIL-SPEC spectrometer at

Andrews Air Force Base to enable a comparison on spectrometer readouts, at a nominal 100 ppm concentration, for

12-element and 20-element blends. An analysis of these

data from five replications is presented in Table 10.

It is of particular interest that the mean values for

seven of the 12 elements are not the same for 12-element and

20-element blends (see Table 11). Only Ag, Cr, Cu, Na, and

Ni give the same values with a 95% confidence.

Sources for the seven discrepancies rest with one or

combinations of three possibilities.

1. Viscosity differences between 12-element and

20-element solutions used in this study,

2. Dilution errors, and

3. Spectral interelement effects.
3. CONCLUSIONS

Nominal concentrations of aluminum, chromium, copper,

iron, lead, magnesium, nickel, silicon, silver, tin and

titanium in oil-base concentrates were validated by chemical

analysis.

Only qualitative descriptions of the effect of variations in viscosity of diluent oil have been reported in the

chemical literature. Thus, the quantitative effects on

spectrometer response attributable to the observed viscosity

differences in this report presently are unknown.

No significant dilution error was observed for 3, 10,

30 and 50 ppm solutions of 12-element standards investigated

by x-ray fluorescence.

A study of long-term stability of Fe, Ni, Cr and Ti

in oil -base solutions has commenced, but sufficient time

has not elapsed for completion of the study.

Limited data indicate that the variance in spectrometer

signals from metallo-organic standards is not significantly

different from the variance in signals produced from usedoil samples.

4. FUTURE WORK

Studies on the long-term stability of diluted calibration standards, described in section 2C, will continue in

fiscal year 1973. However, new investigations will include

solutions containing molybdenum in place of sodium.

The significance of kinematic viscosity and flash point

of oil-base solutions on accuracy and precision of spectrometric measurements with a rotating disk electrode will be

investigated.

Also, error sources in production of calibration

standards and analytical methodology that provides quality

assurance for dilute oil-base solutions will be subjects

for study in fiscal year 1973.

8
APPENDIX A

TABLES - CONCENTRATIONS, PHYSICAL PROPERTIES,

TRACE ELEMENTS, PRECISION STUDIES
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10
Table 2. Analytical methods for NBS chemical analysis

of oil"base concentrates .

Element Method

Aluminum Gravimetric

Chromium Potentiometric

Titration

Copper Gravimetric

Iron Titrimetric

Lead Gravimetric

Magnesium Gravimetric

Nickel Gravimetric

Silicon Gravimetric

Silver Gravimetric

Tin Titrimetric

Titanium Gravimetric

Details

8-hydroxyquinoline

Ammonium persulfateammonium sulfate

Electrodeposition

SnCl

2

reduction followed

by K

2 Cr

2 7

titration

PbSO,; electrodeposition

of soluble lead

Double -precipitation

Mg

2

P

2 ?

Dimethylglyoxime precipitation

Double dehydration with H

2

SO.

AgCl precipitation

Test Lead-KIOCupferron-Ti0

2

11
Table 3. Physical properties of type 245 base oil.

a b Property Measured NBS Supplier

Viscosity at 311 K (100°F) 225 ± 1.8 C 247

(Centistokes) at 372 K (210°F) 17.5 ± 0.2 C 19»3

Flash Point (COC) 534 ± 11 K 522 K

Pour Point 258 K 258 K

Measurements made by cooperating laboratory, Penniman and

Browne, Inc., Baltimore, Maryland.

Provided by Supplier as typical values.

'95% confidence interval* defined i: Triplicate measurements were made.

Arithmetic mean of 3 identical values.

c 95% confidence interval* defined in footnote b of Table 1.

12
3. Table 4. Trace metal content in 245-type base oil

and comparative data for ASTM #1 oil.

Element NBSb Supplier ASTM #1 Oil

Ag 0.01 <0.02 <0.02

Al 1 0.05 <0.02

B 0.05 <0.04 <0.08

Ba 1 <0.08 0.36

Be 0.01 <0.02 <0.02

Cd 0.2 <0.08 <0.08

Cr 0.05 <0.02 <0.02

Cu 0.05 <0.02 <0.09

Fe 1 0.10 0.12

Mg 1 <0.02 0.06

Mn 0.05 <0.08 0.25

Mo 0.01 <0.05 <0.02

Na 0.1 <0.08 <0.08

Ni 0.1 <0.08 0.03

Pb 0.1 0.10 <0.02

Si 1

- - Sn 0.05 <0.05 <0.02

Ti 1 <0.02 0.03

V 0.05 <0.08 <0.08

Zn 5 <0.08 <0.02

aMicrograms of element per gram of oil.

Actual concentrations are less than or equal to these

values.

13
Table 5. Deviation from linear least-squares curve (in ppm) .

Nominal

Concentration

(ppm) Cr

-0.14

Element

Fe Ni

+0.09 -0.10

Ti

3 + 0.12

10 -0.49 -0.08 + 0.10 -0,25

30 + 0.33 + 0.48 -0.40 + 0.62

50 + 0.10 + 0.30 + 0.22 + 0.44

Table 6. Relative deviations from linear

least-squares curve {%)

Nominal

Concentration

(ppm) Cr Fe

Element

Ni T+

3

1 -4.7 + 3.0 -3.3 + 3,9

10 -4.9 -0.8 + 1.0 -2.4

30 + 1.1 + 1.6 -1.4 + 2.1

50 + 0.2 + 0.6 + 0.4 + 0.9

14
Table 7. Analysis of data from reproducibility study

(computer printout)

.

RUN

REPRODUCIBILITY STUDY

MIL SPEC SPECTROMETER* ANDREWS AFB

AG IN D-12 SYNTHETIC STANDARD

STAT ANAL FOR 6

COL: 1

AVERAGE 3.35

MAXIMUM 4*10

MINIMUM 3.20

RANGE .90

ANALYSIS OF VARIANCE

STD. DEV. .23

95 CONF U LIM .35

95 CONF L LIM .16

PCT COEF VAR 6.76

UPPER LIMIT 3.48

LOWER LIMIT 3.22

COLUMNS OF 15

2 3

10.88 31.32

11.60 32.40

10.20 29.40

1.40 3.00

• 38 .98

.59 1.51

.26 .70

3.53 3.14

FOR THE LOT MEAN.

11.10 31.88

10*66 30.76

NUMBERS

4

52.70

55.00

49.60

5.40

1.55

2.38

1.11

2.94

53.59

51.81

COL:

AVERAGE

MAXIMUM

MINIMUM

RANGE

102.80

113*00

93.00

20.00

ANALYSIS OF VARIANCE

STD. DEV. 4.95

95 CONF U LIM 7.59

95 CONF L LIM 3.54

PCT COEF VAR 4.81

269.73

317.00

235.00

82.00

22.94

35.19

16.44

8.51

T TEST... 95 PCT CONF INTERVAL FOR THE LOT MEAN.

UPPER LIMIT

LOWER LIMIT

105.64

99.96

282.89

256.58

15
RUN

REPRODUCIBILITY STUDY

MIL SPEC SPECTROMETER* ANDREWS AFB

AL IN D-12 SYNTHETIC STANDARD

STAT ANAL FOR 7

COL: 1

AVERAGE .09

MAXIMUM 1.00

MINIMUM .00

RANGE 1 .00

ANALYSIS OF VARIANCE

COLUMNS OF 15

2 3

2.10 9.37

3.90 10.60

1.20 8.20

2.70 2.40

NUMBERS

4

26.

30.

26.

4

2fc 80

30

50

STD. DEV. .26 .67 .59 1.54

95 CONF U LIM .40 1.02 .91 2.36

95 CONF L LIM .19 .48 .43 1.10

PCT COEF VAR 281.93 31.69 6*34 5.45

T TEST... 95 PCT CONF INTERVAL FOR THE LOT MEAN.

UPPER LIMIT .24 2.48 9.71 29.10

LOWER LIMIT -.06 1.72 9.03 27.34

COL:

AVERAGE 49.66 99.60 313.53

MAXIMUM 53.40 105.00 322.00

MINIMUM 45.70 92.00 299.00

RANGE 7 . 70 13.00 23.00

ANALYSIS OF VARIANCE

STD. DEV. 2*51 4.26 7.14

95 CONF U LIM 3.86 6.53 10.95

95 CONF L LIM 1.80 3.05 5.12

PCT COEF VAR 5.06 4.27 2.26

T TEST... 95 PCT CONF INTERVAL FOR THE LOT MEAN.

UPPER LIMIT 51.12 102.04 317.63

LOWER LIMIT 48.24 97.16 309.44

16
RUN

REPRODUCIBILITY STUDY

MIL SPEC SPECTROMETER* ANDREWS AFB

CR IN D-12 SYNTHETIC STANDARD

STAT ANAL FOR 6 COLUMNS OF 15 NUMBERS

COL: 1 2 3 4

AVERAGE 2.07 8.89 29.39 50.93

MAXIMUM 3.10 9.40 31.10 54.20

MINIMUM 1.70 8.20 27.50 48.50

RANGE 1.40 1.20 3.60 5.70

ANALYSIS OF VARIANCE

STD. DEV. .37 .36 1.07 1.65

95 CONF U LIM .57 .55 1.64 2.52

95 CONF L LIM .26 .26 .77 1.18

PCT COEF VAR 17.81 4.01 3.64 3.23

T TEST... 95 PCT CONF INTERVAL FOR THE LOT MEAN.

UPPER LIMIT 2.29 9.09 30.01 51.88

LOWER LIMIT 1.86 8.68 28.78 49.99

COL:

AVERAGE 100.00 304.40

MAXIMUM 103.00 321 .00

MINIMUM 96.00 293.00

RANGE 7.00 28.00

ANALYSIS OF VARIANCE

STD. DEV. 2.75 7.12

95 CONF U LIM 4.22 10.92

95 CONF L LIM 1.97 5.10

PCT COEF VAR 2.75 2.34

T TEST... 95 PCT CONF INTERVAL FOR THE LOT MEAN.

UPPER LIMIT

LOWER LIMIT

101.58

98.42

308.48

300.32

17
rIFrWjCIBILITY RUN MIL SPEC SPECTROMETER* ANDREWS AFB

CU IN D-12 SYNTHETIC STANDARD

STAT ANAL FOR 7 COLUMNS OF 15 NUMBERS

COL: 1 2 3 4

AVERAGE • 04 3.21 11*26 32*85

MAXIMUM .10 3.60 11*80 34.50

MINIMUM .00 3*00 10*40 31.20

RANGE .10 • 60 1.40 3*30

ANALYSIS OF VARIANCE

STD. DEV. .05 • 16 • 39 1.06

95 CONF U LIM .08 • 24 • 60 1.63

95 CONF L LIM • 04 • 11 • 28 • 76

PCT COEF VAR 126.77 4.83 3.50 3.24

T TEST... 95 PCT CONF INTERVAL FOR THE LOT MEAN.

UPPER LIMIT • 07 3.30 11.49 33*46

LOV7ER LIMIT .01 3*12 11*03 32*24

COL!

AVERAGE 53.49 103*53 279*27

MAXIMUM 56*60 107.00 300.00

MINIMUM 50*90 99.00 250.00

RANGE 5.70 8.00 50.00

ANALYSIS OF VARIANCE

STD. DEV. 1.48 2.77 15*52

95 CONF U LIM 2.28 4.26 23*81

95 CONF L LIM 1.06 1.99 11*12

PCT COEF VAR 2*78 2*68 5*56

T TEST... 95 PCT CONF INTERVAL FOR THE LOT MEAN.

UPPER LIMIT 54.34 105*12 288.16

LOWER LIMIT 52.64 101*94 270.37

18
RUN

REPRODUCIBILITY STUDY

MIL SPEC SPECTROMETER* ANDREWS AFB

FE IN D-12 SYNTHETIC STANDARD

STAT ANAL FOR 7

COLt 1

AVERAGE

MAXIMUM

MINIMUM

RANGE

.27

.60

.00

.60

COLUMNS OF 15

2 3

2.93 9.69

3.40 10.50

2.50 8.90

.90 1.60

ANALYSIS OF VARIANCE

T TEST... 95 PCT CONF INTERVAL FOR THE LOT MEAN.

COL:

AVERAGE 51*41 104.87 331.73

MAXIMUM 56.40 110.00 360.00

MINIMUM 46.90 96.00 312.00

RANGE 9.50 14.00 48.00

ANALYSIS OF VARIANCE

STD. DEV. 2.45 3.87 12.23

95 CONF U LIM 3.76 5.94 18.76

95 CONF L LIM 1.76 2.77 8.76

PCT COEF VAR 4.77 3.69 3.69

T TEST... 95 PCT CONF INTERVAL FOR THE LOT MEAN.

UPPER LIMIT 52.82 107.09 338.74

LOWER LIMIT 50.01 102.65 324.72

NUMBERS

4

29.81

32.90

27.90

5.00

STD. DEV. • 19 • 23 .55 1.46

95 CONF U LIM .30 .35 • 85 2.24

95 CONF L LIM • 14 .16 .40 1.05

PCT COEF VAR 71.14 7.80 5.70 4.90

UPPER LIMIT .38 3.06 10.01 30.64

LOWER LIMIT .16 2.80 9.38 28.97

19
rIHKoducibility study

mil spec spectrometer* andrews afb

mg in d-12 synthetic standard

STAT ANAL FOR 6 COLUMNS OF 15 NUMB

COL: I 2 3 4

AVERAGE 2.66 10.25 30.80 50.72

MAXIMUM 3.00 11.30 32.90 55.80

MINIMUM 2.40 9.40 28.90 46.50

RANGE .60 1.90 4.00 9.30

ANALYSIS OF VARIANCE

STD. DEV. .15 .59 1.37 3*12

95 CONF U LIM .23 .91 2.10 4.79

95 CONF L LIM • 11 • 43 .98 2.24

PCT COEF VAR 5.65 5.79 4.43 6*16

T TEST... 95 PCT CONF INTERVAL FOR THE LOT MEAN.

UPPER LIMIT 2.75 10.59 31.58 52.51

LOWER LIMIT 2.57 9.91 30.02 48.93

COL:

AVERAGE 100.00 295.67

MAXIMUM 108.00 319.00

MINIMUM 92.00 265.00

RANGE 16.00 54.00

ANALYSIS OF VARIANCE

STD. DEV. 4.87 15.38

95 CONF U LIM 7.47 23.60

95 CONF L LIM 3.49 11.02

PCT COEF VAR 4.87 5.20

T TEST... 95 PCT CONF INTERVAL FOR THE LOT MEAN.

UPPER LIMIT 102.79 304.49

LOWER LIMIT 97.21 286.85

.!..

20
RUN

REPRODUCIBILITY STUDY

MIL SPEC SPECTROMETER* ANDREWS AFB

NA IN D-12 SYNTHETIC STANDARD

STAT ANAL FOR 7

COL: 1

AVERAGE

MAXIMUM

MINIMUM

RANGE

ANALYSIS OF VARIANCE

STD. DEV. .03

95 CONF U LIM .04

95 CONF L LIM .02

PCT COEF VAR 387.30

T TEST... 95 PCT CONF INTERVAL FOR THE LOT MEAN.

COLUMNS OF 15 NUMBERS

2 3 4

01 4.11 11.60 32.59

10 6.60 12.20 33.60

00 3.50 10.90 31.40

10 3*10 1.30 2.20

.75 .37 .59

1.14 .57 .90

.53 .27 .42

18.14 3.19 1*80

UPPER LIMIT .02 4.54 11*81 32.92

LOWER LIMIT -.01 3.69 11.39 32.25

COLs

AVERAGE 54.69 103.33 296.87

MAXIMUM 58.50 114.00 329.00

MINIMUM 51.60 97.00 269.00

RANGE 6.90 17.00 60.00

ANALYSIS OF VARIANCE

STD. DEV. 1.55 5.33 16.78

95 CONF U LIM 2.38 8.17 25.73

95 CONF L LIM 1.11 3.82 12.02

PCT COEF VAR 2.84 5.16 5.65

T TEST... 95 PCT CONF INTERVAL FOR THE LOT MEAN.

UPPER LIMIT 55.58 106.39 306.48

LOWER LIMIT 53.80 100.28 287.25

21
RUN

REPRODUCIBILITY STUDY

MIL SPEC SPECTROMETER* ANDREWS AFB

NI IN D-12 SYNTHETIC STANDARD

STAT ANAL FOR 6

COL: 1

AVERAGE 2.06

MAXIMUM 2*50

MINIMUM 1.40

RANGE 1.10

ANALYSIS OF VARIANCE

COLUMN*J OF 15

2 3

"•*•—— ----

9.15 30.05

9.70 32.60

8.40 28.10

1.30 4.50

NUMBERS

4

52*58

55.60

49.20

6*40

STD. DEV. .28 • 41 1*34 1.88

95 CONF U LIM • 43 • 62 2*05 2.88

95 CONF L LIM .20 • 29 .96 1.34

PCT COEF VAR 13.46 4.43 4.45 3.57

T TEST... 95 PCT CONF INTERVAL FOR THE LOT MEAN.

UPPER LIMIT 2.22 9.39 30.81 53*65

L0V7ER LIMIT 1.90 8.92 29.28 51*51

COL!

AVERAGE 106.27 336.73

MAXIMUM 111.00 355.00

MINIMUM 99.00 313.00

RANGE 12.00 42.00

ANALYSIS OF VARIANCE

STD. DEV. 3.51 11.48

95 CONF U LIM 5.39 17.61

95 CONF L LIM 2.52 8.23

PCT COEF VAR 3.31 3.41

T TEST... 95 PCT CONF INTERVAL FOR THE LOT MEAN.

UPPER LIMIT

LOWER LIMIT

108.28

104*25

343.31

330.15

22
RUN

REPRODUCIBILITY STUDY

MIL SPEC SPECTROMETER* ANDREWS AFB

PB IN D-12 SYNTHETIC STANDARD

STAT ANAL FOR 7 COLUMNS OF 15 NUMB

COLt 1 2 3 4

AVERAGE .28 2.12 9.11 30.79

MAXIMUM 1.00 4.40 10*30 32*50

MINIMUM • 00 .70 6.80 27*80

RANGE 1*00 3.70 3.50 4*70

ANALYSIS OF VARIANCE

STD. DEV. .38 .99 .93 1*22

95 CONF U LIM 58 1*51 1.42 1*87

95 CONF L LIM .27 .71 .67 .87

PCT COEF VAR 135.79 46.53 10.18 3.96

T TEST... 95 PCT CONF INTERVAL FOR THE LOT MEAN.

UPPER LIMIT .50 2.69 9.65 31.49

LOWER LIMIT .06 1*55 8.58 30*09

COL:

AVERAGE 53.23 107.87 292.53

MAXIMUM 56.80 114.00 311*00

MINIMUM 49.70 103.00 279.00

RANGE 7.10 11.00 32.00

ANALYSIS OF VARIANCE

STD. DEV. 2.21 3.25 9.46

95 CONF U LIM 3.40 4.98 14.52

95 CONF L LIM 1.59 2.33 6.78

PCT COEF VAR 4.16 3.01 3*23

T TEST... 95 PCT CONF INTERVAL FOR THE LOT MEAN.

UPPER LIMIT 54.50 109.73 297.96

LOWER LIMIT 51.96 106*00 287.11

23
RUN

REPRODUCIBILITY STUDY

MIL SPEC SPECTROMETER* ANDREWS AFB

SI IN D-12 SYNTHETIC STANDARD

COLUMNS OF 15 NUMBERS

2 3 4

03 2*54 9.77 30.29

10 3.40 10.50 33*40

00 2.00 8.30 28.20

10 1.40 2.20 5.20

STAT ANAL FOR 7

COL: 1

AVERAGE

MAXIMUM

MINIMUM

RANGE

ANALYSIS OF VARIANCE

STD. DEV. .05

95 CONF U LIM .07

95 CONF L LIM .03

PCT COEF VAR 146.39

T TEST... 95 PCT CONF INTERVAL FOR THE LOT MEAN.

.37 • 65 1.59

.56 .99 2.44

.26 .46 1.14

14.49 6.64 5.24

UPPER LIMIT .06 2.75 10.15 31*20

LOWER LIMIT • 01 2.33 9.40 29.38

COL:

AVERAGE 52.05 103.80 304.80

MAXIMUM 56.40 110.00 324.00

MINIMUM 48.30 96.00 291.00

RANGE 8.10 14.00 33.00

ANALYSIS OF VARIANCE

STD. DEV. 2.17 3.78 9.47

95 CONF U LIM 3.34 5.80 14.52

95 CONF L LIM 1.56 2.71 6.78

PCT COEF VAR 4.18 3.64 3.11

T TEST... 95 FCT CONF INTERVAL FOR THE LOT MEAN.

UPPER LIMIT 53.29 105.97 310.23

LOWER LIMIT 50.80 101.63 299.37

24
RUN

REPRODUCIBILITY STUDY

MIL SPEC SPECTROMETER* ANDREWS AFB

SN IN D-12 SYNTHETIC STANDARD

STAT ANAL FOR 6 COLUMNS OF 15 NUMBERS

COL: 1 2 3 4

AVERAGE .10 5.93 26.24 48.17

MAXIMUM .80 7.40 28.00 52.10

MINIMUM .00 4*10 23.70 45.30

RANGE • 80 3.30 4.30 6*80

ANALYSIS OF VARIANCE

STD. DEV. • 25 I. 00 1.37 2.35

95 CONF U LIM .38 1.53 2.11 3.61

95 CONF L LIM .18 .71 .98 1.68

PCT COEF VAR 247.85 16.81 5.23 4.88

T TEST... 95 PCT CONF INTERVAL FOR THE LOT MEAN.

UPPER LIMIT .24 6.50 27.03 49.51

LOWER LIMIT -.04 5.36 25.45 46.82

COL:

AVERAGE 100.33 308.40

MAXIMUM 105.00 315.00

MINIMUM 92.00 300.00

RANGE 13.00 15.00

ANALYSIS OF VARIANCE

STD. DEV. 3.94 5.07

95 CONF U LIM 6.04 7.77

95 CONF L LIM 2.82 3.63

PCT COEF VAR 3.93 1.64

T TEST... 95 PCT CONF INTERVAL FOR THE LOT MEAN.

UPPER LIMIT 102.59 311.31

LOWER LIMIT 98.07 305.49

25
BUN

REPRODUCIBILITY STUDY

MIL SPEC SPECTROMETER, ANDREWS AFR

TI IN D-12 SYNTHETIC STANDARD

STAT ANAL FOR 6 COLUMNS OF 15 NUMBERS

COL: 1 2 3 4

— — *>«r »••— ---- *•«•"» — ««^

AVERAGE 2.28 9.45 29.49 49.65

MAXIMUM 2.60 10.10 31.70 53.70

MINIMUM 1*60 8.70 27.30 45.20

RANGE 1.00 1.40 4.40 8*50

ANALYSIS OF VARIANCE

STD. DEV. • 23 .46 1.40 2*53

95 CONF U LIM .36 .71 2.15 3.88

95 CONF L LIM • 17 .33 1*00 1.81

PCT COEF VAR 10.25 4.88 4.75 5.10

T TEST... 95 PCT CONF INTERVAL FOR THE LOT MEAN.

UPPER LIMIT 2*41 9.71 30.29 51.10

LOWER LIMIT 2.15 9.18 28*68 48.20

COL:

AVERAGE

MAXIMUM

MINIMUM

RANGE

102.33

107.00

95.00

12.00

293.40

306.00

273.00

33.00

ANALYSIS OF VARIANCE

STD. DEVf 3.96

95 CONF U LIM 6.07

95 CONF L LIM 2.84

PCT COEF VAR 3. 87

9.75

14.95

6.98

3.32

T TEST... 95 PCT CONF INTERVAL FOR THE LOT MEAN.

UPPER LIMIT

LOWER LIMIT

104.60

100.06

298.99

287.81

26
Table 8. Analysis of data from used-oil samples

(computer printout)

>RUN

REPRODUCIBILITY STUDY MIL SPEC SPECTROMETER* ANDREWS AFB

USED LUB OIL SAMPLE MIL-L-22851 FROM RECIP ENGINE

COLUMN CODE* 1-FE 2-AG 3-AL 4-CR 5-CU 6-MG 7-NA 8-NI

STAT ANAL FOR 8 COLUMNS OF 15 NUMBERS

COLl 1 2 3 4 .-.. ---- .... *»"•—*» •**

AVERAGE 32*62 .13 7.76 1.83

MAXIMUM 36.00 .80 9.80 2.40

MINIMUM 30.60 .00 6*10 1*30

RANGE 5*40 .80 3.70 1.10

ANALYSIS OF VARIANCE

STD. DEV. 1.48 • 19 .78 • 31

95 CONF U LIM 2.27 • 29 1.19 • 48

95 CONF L LIM 1.06 • 13 • 56 • 22

PCT COEF VAR 4.53 140.79 10.03 17.12

T TEST... 95 PCT CONF INTERVAL FOR THE LOT MEAN.

UPPER LIMIT 33.47 • 24 8.21 2.01

LOWER LIMIT 31.77 • 03 7.31 1*65

COLX

AVERAGE 13*44 • 81 1 .91 9.30

MAXIMUM 15*30 1.40 2 .50 10.30

MINIMUM 12.70 .70 1 .70 8*00

RANGE 2.60 • 70 .80 2.30

ANALYSIS OF VARIANCE

STD. DEV. .59 • 18 .21- • 55

95 CONF U LIM .91 • 28 .32 • 85

95 CONF L LIM .42 • 13 • 15 • 40

PCT COEF VAR 4.41 22.22 10 .98 5.96

T TEST... 95 PCT CONF INTERVAL FOR THE LOT MEAN • UPPER LIMIT 13.78 • 92 2 .03 9.62

LOWER LIMIT 13.10 .71 1 .79 8.98

27
RUN

REPRODUCIBILITY STUDY MIL SPEC SPECTROMETER* ANDREWS AFB

USED LUB OIL SAMPLE MIL-L-22851 FROM RECIP ENGINE

COLUMN CODE: 1-PB 2-SI

STAT ANAL FOR 2 COLUMNS OF 15

COL: 1 2 3

AVERAGE 343.73 3.11

MAXIMUM 362.00 3.60

MINIMUM 323.00 2.70

RANGE 39.00 .90

NUMBERS

4

ANALYSIS OF VARIANCE

STD. DEV. 11.65 .29

95 CONF U LIM 17.87 .45

95 CONF L LIM 8.35 .21

PCT COEF VAR 3.39 9.47

T TEST... 95 PCT CONF INTERVAL FOR THE LOT MEAN.

UPPER LIMIT 350.41 3.28

LOWER LIMIT 337.05 2.94

28
RUN

REPRODUCIBILITY STUDY MIL SPEC SPECTROMETER* ANDREWS AFB

USED LUB OIL SAMPLE MIL-L-23699 FROM JET ENGINE

COLUMN CODE I 1 -FE*2-CU*3-SI ,4-SN,5-TI

STAT ANAL FOR 5

COL: 1

AVERAGE

MAXIMUM

MINIMUM

RANGE

COLUMN'> OF 15 NUMBERS

2 3 4

72 .11 3.25 5.35

10 .30 4.00 7.00

40 .00 2.40 3.60

70 .30 1.60 3*40

ANALYSIS OF VARIANCE

STD. DEV. .22 .09 .47 1.03

95 CONF U LIM .34 • 14 .73 1.57

95 CONF L LIM .16 .06 .34 .73

PCT COEF VAR 31.15 82.85 14.60 19.18

T TEST... 95 PCT CONF INTERVAL FOR THE "LOT MEAN.

UPPER LIMIT

LOWER LIMIT

.85

• 59

.16

.06

3.53

2.98

5.93

4.76

COL:

AVERAGE

MAXIMUM

MINIMUM

RANGE

.03

.10

.00

.10

ANALYSIS OF VARIANCE

STD. DEV. .05

95 CONF U LIM .07

95 CONF L LIM .03

PCT COEF VAR 146.39

T TEST... 95 PCT CONF INTERVAL FOR THE LOT MEAN.

UPPER LIMIT

LOWER LIMIT

.06

.01

29
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30
Table 10. Analysis of data for comparison of spectrometer

response for 12-element and 20-element blends

(computer printout)

>RUN

REPEATABILITY RUN

D-20 SYNTHETIC STANDARD

COLUMN CODE: 1-MN 2-MO 3-V 4-ZN

STAT ANAL FOR 4 COLUMNS OF 5 NUMBERS

COL: 1 2 3 4

AVERAGE 60*80 61.00 77.80 23.20

MAXIMUM 82.00 62.00 79.00 25.00

MINIMUM 80.00 60*00 75.00 21.00

RANGE 2.00 2.00 4.00 4.00

ANALYSIS OF VARIANCE

STD. DEV. • 84 1.00 1.79 1.48

95 CONF U LIM 2*15 2*57 4.59 3.81

95 CONF L LIM .47 • 56 1.00 • 83

PCT COEF VAR 1.04 1*64 2.30 6.39

T TEST... 95 PCT CONF INTERVAL FOR THE LOT MEAN.

UPPER LIMIT 81.96 62.39 80.28 25*26

LOVER LIMIT 79.64 59.61 75.32 21*14

31
>RUN

REPEATABILITY RUN

D-20 SYNTHETIC STANDARD

COLUMN CODE: 1-NI 2-PB 3-SI 4-SN 5-TI 6-B 7-BA 8-CD

COL:

STAT ANAL FOR 8 COLUMNS OF 5 NUMBERS

COL: 1 2 3 4 ---- .... -— - — »••> —

AVERAGE 101.00 111.00 106.00 107.60

MAXIMUM 102.00 114.00 108.00 110.00

MINIMUM 100.00 109.00 104.00 106*00

RANGE 2.00 5-00 4.00 4.00

ANALYSIS OF VARIANCE

STD. DEV. .71 1.87 1.58 1.52

95 CONF U LIM 1.82 4.80 4.06 3*89

95 CONF L LIM .40 1.05 .88 • 85

PCT COEF VAR .70 1.69 1.49 1.41

T TEST... 95 PCT CONF INTERVAL FOR THE LOT MEAN.

UPPER LIMIT 101.98 113.60 108.19 109.71

LOVER LIMIT 100.02 108.40 103*81 105*49

AVERAGE 91.00 64.60 81.00 50.00

MAXIMUM 93.00 66.00 85.00 51.00

MINIMUM 89.00 62.00 78.00 49.00

RANGE 4.00 4.00 7.00 2.00

ANALYSIS OF VARIANCE

STD. DEV. 1.58 1.64 3.24 .71

95 CONF U LIM 4.06 4.22 8.32 1.82

95 CONF L LIM .88 .92 1.81 .40

PCT COEF VAR 1.74 2*54 4.00 1 .41

T TEST... 95 PCT CONF INTERVAL FOR THE LOT MEAN.

UPPER LIMIT 93.19 67.08 85.50 50.98

LOWER LIMIT 88.81 62.52 76.50 49.02

32
>RUN

REPEATABILITY RUN

D-20 SYNTHETIC STANDARD

COLUMN CODE: l-FE 2-AG 3-AL 4-BE 5-CR 6-CU 7-MG 8-NA

STAT ANAL FOR 8 COLUMNS OF 5 NUMBERS

COL: 1 2 3 4 .... .... .... .... ....

AVERAGE 102.80 100.00 102.00 62.60

MAXIMUM 104.00 103.00 103.00 63.00

MINIMUM 101*00 97.00 100.00 61.00

RANGE 3.00 6.00 3.00 2.00

ANALYSIS OF VARIANCE

STD. DEV. 1.30 2.55 1.22 .89

95 CONF U LIM 3.35 6*54 3.14 2.30

95 CONF L LIM .73 1.43 .68 .50

PCT COEF VAR 1.27 2.55 1.20 1.43

T TEST... 95 PCT CONF INTERVAL FOR THE LOT MEAN.

UPPER LIMIT 104.61 103.54 103.70 63.84

LOWER LIMIT 100.99 96.46 100.30 61.36

COL:

AVERAGE 100.80 98.80 100.40 104.20

MAXIMUM 102.00 100.00 103.00 115.00

MINIMUM 99.00 96.00 97.00 100.00

RANGE .

,

c 3.00 4.00 6*00 15.00

ANALYSIS OF VARIANCE

STD. DEV. 1.30 1.79 2.30 6.57

95 CONF U LIM 3.35 4.59 5.91 16.87

95 CONF L LIM .73 1.00 1.29 3.67

PCT COEF VAR 1.29 1.81 2.29 6.31

T TEST... 95 PCI' CONF INTERVAL FOR THE LOT MEAN.

UPPER LIMIT 102.61 101.28 103.60 113.32

LOWER LIMIT 98.99 96.32 97.20 95.08

33
>RUN

REPEATABILITY RUN

D-12 SYNTHETIC STANDARD

COLUMN CODE: l-FE 2-AG 3-AL 4-CR 5-CU 6-MG 7-NA 8-NI

STAT ANAL FOR 8 COLUMNS OF 5 NUMBERS

COL: 1 2 3 4 ---- *»»»«** .... • •_- tmlititM

AVERAGE 100.60 99.00 95.80 99.80

MAXIMUM 105*00 100.00 102.00 104.00

MINIMUM 98*00 95.00 92.00 96*00

RANGE 7.00 5*00 10.00 6.00

ANALYSIS OF VARIANCE

STD. DEV. 3*21 2.24 3.77 2.68

95 CONF U LIM 8.24 5.74 9.67 6.89

95 CONF L LIM 1.79 1.25 2.11 1.50

PCT COEF VAR 3*19 2.26 3.93 2.69

T TEST... 95 PCT CONF INTERVAL. FOR THE LOT MEAN.

UPPER LIMIT 105.05 102.10 101.03 103*52

LOWER LIMIT 96.15 95.90 90.57 96*08

COL:

AVERAGE 100.40 95.80 105*20 100.20

MAXIMUM 104.00 101.00 115.00 105*00

MINIMUM 99.00 93.00 100.00 98.00

RANGE 5.00 8.00 15.00 7.00

ANALYSIS OF VARIANCE

STD. DEV. 2.07 3.11 6*14 3*19

95 CONF U LIM 5.32 7.99 15.76 8.20

95 CONF L LIM 1.16 1.74 3*43 1*79

PCT COEF VAR 2.07 3.25 5*84 3*19

T TEST... 95 PCT CONF INTERVAL, FOR THE LOT MEAN.

UPPER LIMIT 103*28 100.12 113.72 104*63

LOWER LIMIT 97.52 91.48 96*68 95*77

34
>RUN

REPEATABILITY RUN

D-12 SYNTHETIC STANDARD

COLUMN CODE: 1-PB 2-SI 3-SN 4-Tl

STAT ANAL FOR 4 COLUMNS OF 5 NUMBERS

COL: 1 2 3 4 .... --.-- ••«- •«•«• ....

AVERAGE 107.20 99*20 99*60 96.80

MAXIMUM 110*00 104.00 106.00 102.00

MINIMUM 105.00 96.00 97.00 93.00

RANGE 5.00 8.00 9*00 9.00

ANALYSIS OF VARIANCE

STD. DEV. 2*28 3*96 3*63 3*63

95 CONF U LIM 5.85 10.17 9.33 9.33

95 CONF L LIM 1*27 2*21 2*03 2.03

PCT COEF VAR 2.13 3*99 3*64 3.75

T TEST*.. 95 PCT CONF INTERVAL. FOR THE LOT MEAN.

UPPER LIMIT 110.37 104*70 104.84 101*84

LOWER LIMIT 104.03 93*70 94.76 91.76

35
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36
APPENDIX B

FIGURES - ANALYTICAL RESPONSE FUNCTIONS BY X-RAY

FLUORESCENCE (XRF) AND OPTICAL EMISSION SPECTROMETRY (OES)

37
0I1VU AJ.ISN31NI 3M1V13U
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39
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40
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41
10 30 100

CONCENTRATION (ppm)

300

Figure 5. Analytical response functions for sodium, nickel,

and lead by optical emission spectrometry.

42
10 30 100

CONCENTRATION (ppm)

300

Figure 6. Analytical response functions for silicon, tin,

and titanium by optical emission spectrometry.

43
Figure 7

10 30 100

CONCENTRATION (ppm)

Analytical response functions for chromium, copper,

and magnesium by optical emission spectrometry.

44
1 1 l 1 1

o Fe

300 a Ag

D Al —

O

fe ioo

E

INTENSITY o —

RELATIVE

OJ

o —

1 a | 1 i i

1 10 30 100

CONCENTRATION (ppm)

300

Figure 8 Analytical response functions for iron, silver,

and aluminum by optical emission spectrometry.

45
FORM NBS-U4A (1-7!) 2. Gov t Accession No.

U.S. DEPT. OF COMM. BIBLIOGRAPHIC DATA

. SHEET

1. PUBLICATION OR REPORT NO. NBS TN-751

3. Recipient's Accession No.

4. TITLE AND SUBTITLE

( Studies of Calibration Standards Used in

the Department of Defense Equipment Oil Analysis

Program

5. Publication Date January 1973

6. Performing Organization Code

7. AUTHOR(S)

Danold W. Golightly and Jpseph L. Weber, Jiu.

9. PERFORMING ORGANIZATION NAME AND ADDRESS

NATIONAL BUREAU OF STANDARDS

DEPARTMENT OF COMMERCE

WASHINGTON, D.C. 20234

8. Performing Organization

10. Project/Task/ Work Unit No. 31Q 2421

11. Contract/Grant No.

12. Sponsoring Organization Name and Address Naval Air Systems Command

Department of the Navy

Crystal Plaza 5 Alexandria, Va.

13. Type of Report & Period Covered Final - FY 72

14. Sponsoring Agency Code

15. SUPPLEMENTARY NOTES

16. ABSTRACT (A 200-word or less factual summary of most significant information. If document includes a significant

bibliography or literature survey, mention it here.) At the request of the Naval Systems Air Command, Department of the

Navy, studies have been conducted on organo-metallic calibration

standards and diluent oil used in the Department of Defense Equipment

Oil Analysis Program. Consultation on standards has been provided,

and measurements of physical properties of base oil, concentrations

of major elements in standards, concentrations of trace contaminants,

and stability of solutions have been performed. Results of studies

accomplished in fiscal year 1972 are detailed in this report.

17. key words (Alphabetical order, separated by semicolons) Calibration standards; concentration

validity; flash point; lubricating oil; pour point; spectrometric

analysis; stability; trace elements; viscosity.

18. AVAILABILITY STATEMENT

Fl UNLIMITED.

I I FOR OFFICIAL DISTRIBUTION. DO NOT RELEASE

TO NTIS.

19. SECURITY CLASS

(THIS REPORT)

UNCLASSIFIED

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(THIS PAGE)

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21. NO. OF PAGES

22. Price

$.75 Domestic Postpaid $.50 GPO Bookstore

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National Bureau of Standards

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215