_____--_

f - ------
V A S A TECHNICAL TRANSLATION -7 --._______

NASA TT F- 11,483

I
Translation o f an a r t i c l e from
Japan Analyst, V. 16, No. 10, pp. 1050-1055, 1967

(4")

GPO PRICE $

CFSTI PRICE(S) 8

Microfiche (MF) - 6 5'-

ff 663 July 66

NATIONAL AERONAUTIC3 SPACE ADMINISTRATION

WASHINGTON, D. C. FEBRUARY 1968

I----- L 1 -_-
Even Roman odd
 !-

L
5 i-
t-

10 E
I-
t
I

l5 I-

*O
1'
L1--
oxides were a l s o s t u d i e d f o r .:heir far i n f r a r e d s p e c t r a

These oxides were found t o have s p e c i f i c a b s o r p t i o n s i n

t h e measured r e g i o n , and showed d e f i n i t e c o r r e l a t i o n s between
t h e i r s p e c t r a and c r y s t a l s t n . c t u r e s .

25 F-
E
30
35 F bond can be e a s i l y c a l c u l a t e d as a d i a t o m i c molecule: e . g . ,
t h a t of f e r r i c o x i d e , FeO, was 1.24 md/A.
(4) Spinnel (MgA1,0,) type o x i d e s have c o u p l i n g a b s o r p t i o n

of n o n m e t a l l i c
that the
31t was r e c o g n i z e d , moreover,
and q u a n t i t y S i 0 2 were l i n e a r l y
,
I

correlated.
40 I_
Introduction
Among t h e b a s i c s t u d i e s t o s t e e l and i r o n , t h o s e which r e l a t e /10503
o x i d e s are i n d i s p e n s i b l e . Such a r e t h e o b j e c t of i n v e s t i g a t i o n s ,
r t i c u l a r l y i n t o inclusions i n t h e p r e s e r v a t i o n of s t e e l and
e s u r f a c e t r e a t m e n t of s t e e l hand, owing t o t h e f a c t that.
f r a r e d a b s o r p t i o n methodology t h e p r e s e n c e of
i
I n f r a r e d Absorption Spectrum S t u d i e s o f I r o n and S t e e l (Report No. 1 ) .
2Yawata S t e e l Co. Ltd., Tokyo Research I n s t i t u t e , I i d a , Kawasaki C i t y ,
50 - Kanagawa P r e f e c t u r e .
l-3Numbers
- -._- - - i-n- t h e margin i n d i-c a__-
te i n t h e foreiRn t e x t . __I ..
-
El.
Even
u
Roman
1
odd
 ! _--_^----
I _ _-- - I_ --I-- _ _--
:amorphous m a t e r i a l s , which cannot be i n i e s t i g a t e d through t h e u s e of x - r a y
!
C d i f f r a c t i o n and o t h e r t e c h n i q u e s , t h e u i l i z a t i o n of i n f r a r e d a b s o r p t i o n spec-
itsoscopy i s a n t i c i p a t e d i n t h e PagarQnapjii&Qels t u d i e s . On t h e b a s i s
b a s o n i n g , lthe writers s e l e c t e d 25 oxides whose p r e s e n c e i n s t e e l was

i-
I
t
5 !These oxid s were s u b j e c t e d t o absorption anal

I n f r a d e d a b s o r p t i o n spectrum d a t a t h a t have been accumulated i n t h e p a s t

lo
6
ave been l i m i t e d p r i n c i p a l l y t o a body1 of i n f o r m a t i o n i n v o l v i n g t h e i n o r g a n i c
mpounds. Some r e p o r t s have appeared i n g e n e r a l s t u d i e s [l-31 and i n books
1, b u t t h e r e i s l i t t l e l i t e r a t u r e concerning t h e oxides and what i s
a i l a b l e i s o n l y r e p r e s e n t a t i v e i n n a t q r e . There a r e v i r t u a l l y no i n t e g r a t e d
k t u d i e s of t h i s s u b j e c t . The s u b j e c t s of physico-chemical t r e a t m e n t ,
p a r t i c u l a r l y f o r c e c o n s t a n t s and c a l c u l + t i o n s of normal v i b r a t i o n s a r e v i r t u a l 1

k1
v i r t u a l l y untouched. We know
l5 f d i v a l e n t m e t a l s , such as t h
annous oxide [6] [7] , cerium
3 , t e l l u r i u m oxide [ 8 ] , barium
p r i c o x i d e [12] and n i c k e l oxide [13
20 I n r e c e n t y e a r s many s t u d i
W f r a r e d a b s o r p t i o n of c o r r o s i o
lment of t h i s f i e l d a r e f a b o r a b l
awa and Terade [15] , f o r ex
ncerning t h e i n f r a r e d absorptio
ading i n t o b a s i c s t u d i e s of t h e
i n v e s t t p t *e-comEtxt
t a l s t r u c t u r e of 25 r e p r e s e
i c a t i o n of t h i s d a t a t o che
e s t u d i e s of t h e o x i d e s
n monoxide [SI , [6]
x i d e [SI, selenium oxide
sium o x i d e [9] [ l l ] , z i n c o x i d e ,
i s h e d on t h e s u b j e c t of t h e
p e c t s f o r t h e f u r t h e r develop-
u d i e s of Matsutaka [14] and
s of s y n t h e s i z i n g d a t a
o x i d e s , and as a means of
and s t e e l , t h e a u t h o r s
ion on s p e c t r a and t h e
as w e l l a s t h e p o s s i b l e

2 . 1 Measurements
In a p p l y i n g t h e potassium e , 1 mg of t h e t e s t
l e s was mixed w i t h 300 mg bromide. This was
a r e d i n p e l l e t form f o r t h otassium bromide powder
had been prepared by powd i n a g r i n d e r m i l l and
i n g t h e powder i n a vacuum a y s . The normal methods
e followed when t h e Nujol p d. For measurements i n
extreme i n f r a r e d s p e c t r a a elow, t h e kneaded
y e t h y l e n e method was used.

P r o p e r l y , t h e s p e c t r a should have d i v i d e d above and below 400 cm-l

r p r e s e n t a t i o n , however, i n
shown i n t h e same c h a r t s

t The equipment used was a Perkins-E

e c t r o s c o p e and t h e FIS-1 and F I S - 2 1
Grating

e c t r o s c o p e used t o g e t h e r . The
bout 7 - 167 p).
_.__ _-__ -_ -

1-2-- L 1
Even Roman odd
 12.2 Test Materials Page One T i t l e
i - 1
c The m terials tested are the 25 ty les of metal oxides given in T
samples.were of comm&V5%lPg %d~~tk6nfirmationof their
k s by x-ray diffraction. /lo51

10 TABLE I . METAL OXIDE SAMPLES

1
I

No. Sample Purity Identificatiant

I Aluminum oxide, A1101 In grade 8-AI:OI
15 2 Calcium oxicle, CaO I c.0
3 Ceric oxide. 002 99.!l9* CeO:
4 Cobalt oxide, Coioc 99.9% ColO4tt
5 Chromium trioxide, c.0~ Beat purity Croitt
6 Chromic oxide, Cr:Ol - CrKh
7 Cupric oxidel CuO - CUO

20
Ferrous oxide. FeO - FeO
9 Ferric oxide. Fez03 Special & a-FeiUs
10 Fmoric oxide, FesOc Irt grade FeiOi
11 Magme&, MgO - hlgO
I2 b l a n g r + oxide, XlnO 99.9% MnO
U Nickel oxide, NiO W.9s NiO
14 Lead mnoxide. PbO lit grade Pbott
25 10 L a d &oxide. PbO: 1st grade PbOi
I4 Scandium oxide, Sc201 99.9%
11 QUI"I, SiO,
IIt wade
%io3
a-SiO: - -
1 Stannous oxide, SnO 99% up SnO
H - S c d oxide. SnO: 99% up SnO:
T i t a n k oxide. Ti01 Inp.de Ti02 (k.w)
91 Vanadium rsquioxide, V:O, W vzorttt
30 22 Vanadium pentoxide, V201
23 Yttrium oxide, YIO, 95.9% Y:Oa
- 14 Zinc oxide, ZnO 1st wade 2110
25 Zmanium oxide, Z r O a
t Idcnt(bd by mum d Y @ q YIlrutioD method, tt Unknown

35

40

45

50

i r - L l 3
Even Roman odd
 I
Wave number, an-1

F i gure 2 . I n f r a r e d Absorption
Spectr o f Metal Oxides ( P a r t 11)
- . (4")

-
30 -
The i n f r a r e d a b s o r p t i o n s p e c t r a i t a i n e d f o r t h e 25 oxides are given
i n F i g u r e 1 through 5 . I t was apparen t h a t v i r t u a l l y a l l o f t h e t e s t samples
-
e x h i b i t e d c h a r a c t e r i s t i c a b s o r p t i o n p r ierties w i t h i n t h e measured r e g i o n s
4 4 0 0 -- 1,400 cm-'). I t was a l s o n o t e t h a t when 10 of t h e oxides were
35 - r e s t e d i n t h e extreme i n f r a r e d r e g i o n 60 - - 400 c m - l (25-166 p), t h e y a l l '
-demonstrated i n d i v i d u a l c h a r a c t e r i s t i c i b s o r p t i o n p r o p e r t i e s . These 10
-exides were t r i c o b a l t t e t r o x i d e , chrom m oxide, c u p r i c oxide, z i n c oxide,
s t a n n o u s oxide, stannous d i o x i d e , t i t a tum oxide , vanadium pentoxide, y t t r i u m
-oxide, and zirconium oxide. T h e i r cha i c t e r i s t i c absorption s p e c t r a a r e
40 -shown i n c o n s o l i d a t e d form i n Tables I1 md 111.
t

d i s c r e p a n c i e s were seen between t h e absorption p o s i t i o n s o b t a i n e d through

potassium bromide d i s k method and those o b t a i n e d u s i n g t h e Nujol p a s t e
ethod.

. Discussion

p-
Even
uRoman
-
odd
 I
-_ I_
__
kexcept f o r an a b e r r a t i o n i n t h e v i c i n i y of 400 cm (25 u thought t o be
I I and '1052
f;e;:ainai----ea- r taoc tveirbirsat ti icona sb soofr pa
t icgag'9
pos' t i o n se do n o t o v e r l a p ,
a t f o r t h i s reason, t h e y wo Id b e e f f e c t i v e f o r u s e i n qua i t a t i v e

f
Cover l m a e e x c e p t where t h e
broad. There i s ,
d' f f i c u l t y i n d i s c r i m i n a t i n g between t h e
c mpounds whose c r y s t a l l i n e s t r u c t u r e
[17] i s similar, p a r t i c u l a r l y t h o s e
oxides of t h e d i v a l e n t metals whose
adsorption s p e c t r a are broad and l i e i n
v i c i n i t y o f 400 cm-1. Mixed samples,
have broad and overlapping
making d i s c r i m i n a t i o n

4.1 The Iron Oxides

o r e s and c o r r o s i o n
a v e b e e n d-s tn
a-ferric

30 F i g u r e 3. I n f r a r e d Absorption
S p e c t r a of Metal Oxide (Part 111).
-
F u r t h e r , according t o Maekawa
ifferences i n the spectroscopic
x i d e w i t h i n t h e 5-30 p range.
b s e r v a t i o n s w i t h i n t h e 50-400
he ranges are broad, b u t t h a t
because t h e i r i n f r a r e d
a2 [ l S ] , t h e r e are r e c o g n i z a b l e
t i o n o f a - f e r r i c oxide and Y-ferric
n a l l y , Matsutaka [14] has made
-200 u) r e g i o n . He h a s r e p o r t e d t h a t
i s low. Thus, i n f r a r e d a b s o r p t i o n /lo53

1
- 1

-spectroscopy i s f u l l y adequate f o r use i n t h e s t u d y o f s t e e l i f t h e

40 -characteristic a b s o r p t i o n o f t h e oxyac'ds (a-FeOOH, e t c . ) are u t i l i z e d
t o g e t h e r with t h o s e of t h e i r o n oxides.
-
.2 The Oxides o f Chromium, Lead, Tin land Vanadium
I

i
45 - A l l of t h e s e oxides were s t u d i e d i n two d i f f e r e n t samples i n which t h e
v a l e n c e o f t h e metal component d i f f e r e . Owing t o t h e f a c t t h a t t h e
t o o r d i n a t i o n numbers were d i f f e r e n t , t e crystalline structures also differed
- g r e a t l y . I t i s apparent t h a t i t i s ea y t o d i s c r i m i n a t e between them,
-because t h e y a l l have c l e a r l y d i f f e r % a b s o r p t i o n c h a r a c t e r i s t i c s . The
50 a b s o r p t i o n o f chromium oxide at 448 an *419 cm-l i s p e c u l i a r , making t h i s
-
I__ - _. __

E- U
Even Roman odd
 -_ -
+ABLE 111 S p e c t r a l P o s i t i o n s of I n f r a ed Absorption Bands of Metal O x i d e s . - - l

-t
-
- ( P a r t 11)
-1Ooonn-~ rncm-' WX)cm-l 7M)cm-1 Sa)cm-1 500cm-1 1ooCm-1
-
L
- - --
5 -
+
Uvaiartrn a i d e . r - N &
Calcium oxide, G O
Ceric oxide, CeO,
-
-
-
- - -
mo(1)

-
=(a)
-
-
SBs(1)
-- 492(m),4al*3
m(1)
-46060m)t
I
r
Chmuiun trioxide, CrOa lW5 (m) 3AI' w 2 ( a ) * 830 ( w ) 735 (m) - - -
Ferrous oxide, FeO - - - - - - 410 (m)
7 - - - -
10
1 Ferrx oxide, r-FerO,
Ferrosic oxide, FesO,
M-rn oxide, MgO
-
-
-
-
-
-
-
-
-
-
-
543 ( I )
seo(1)
-
472 (m)

--(a)
-
Manganese oxide, Ma0 - - - - - - *a). 4ll(ah)
- - - - - -
t Nickel oxidc, NiO
L e d W , P b O ,
Scandium oxide, SctO,
1388(w)
-
-
-
-
-
-
-
- -
630 (m) -590 (ah)t
448(m)

435 ( )
-
- -
Slim dioxide, a-SiO,
Vanadium scsquioxide, VI03 -
1170(m), 1089( a )

-
-
-
-
-
799(m), 780(m)
-
-
697 (m)
-
511 (m)
540(w)t
160 ( a )
-
Zinc oxidc. 7.110 - 530(r) 4W*),ufJ(*)
t Ther values Here obtained by meana of nujol paste method.
-
' 1 5 ~
h a r a c t e r i s t i c e f f e c t i v e f o r uyov,,2$, +%c&xtremely i n t e r e s t i n g , looking

F
t t h e vanadium o x i d e s , t h a t t h e r e 1s c e a r a b s o r p t i o n by vanadium

-+
r i o x i d e , b u t , conversely, vanadium p e r t o x i d e h a s f o u r h i g h a b s o r p t i o n
2o - p o s i t i o n s . Chromium t r i o x i d e i s q u i t e u n s t a b l e i n t h e a i r . However, a
was o b t a i n e d and t h i s i s i n d i c a t e d i n t h e graph. I t i s q u e s t i o n a b l e ,
owever, whether o r n o t t h e d a t a p e r t a i n i n g t o t h i s a b s o r p t i o n are completely
I____
(4")

There is only one c h a r a c t e r i s t i c a b s o r p t i o n at about 400 c m - l (25 p)

o x i d e , calcium oxide, f e r r o u s oxide and s o f o r t h . These
ompounds are a l s o q u i t e simple i n c o n s t r u c t i o n . The v a r i o u s p h y s i c a l con-
t a n t s f o r t h e s e materials are easy t o c a l c u l a t e when they are considered as
To give an example, i n t h e case o f f e r r o u s oxide t h e
i
p o s i t i o n i S 410 cm-l. Using t h i s wavelength as a ,
35
ase, i t s f o r c e c o n s t a n t may be c a l c u l a t e d a t 1.24 md/A [16]. /lo54

There are a l a r g e number of b e r t compounds i n t h e s e types o f

r e s u l t there are differences
40 i n t h e i r l a t t i c e constants. they are of simple c o n s t r u c t i o n ,
i s b e l i e v e d t h a t ,the o f t h e i r o n oxides, which
v i r t u a l l y unknown, may well commence with t h e s e compounds.

The S p i n e l Group Oxides

45
T r i i r o n t e t r o x i d e and t r i c o b a l t are c l a s s i f i e d as s p i n e l
o x i d e s . These types common i n f r a r e d
p a t t e r n s . Be coupled c h a r a c t e r i s t i c
i s apparent i n t h e 300-600 [18] [19].
50

E-- U
Even Roman odd ~
 100, _I_I_______T_

5 loo, I

2
I
I

t----
-
.-
wave numbs, an-1

i g u r e 4 . I n f r a r e d Apsorption
I

p e c t r a o f Metal Oxides ( P a r t IV)

--
- - -
I
Figure
of Meta
1. Wave number, crn-1

t f i a r e d Absorption S p e c t r a
0 ' d s ( P a r t V)

-
30 -
-
TABLE I1 S p e c t r a l P o s i t i o n s of I n f r a r d Absorption Bands o f Metal Oxides.

45

50
I- NAP
I- U 7
Even Roman odd
 __._I_----- I_

-------

--T-
i
,
I__---

- Waldron [19] performed s t u d i e s o a series o f f e r r i t e s (MFe204:

i-M = Co, F e y Mg, Mn, N i , Zn, et$>&, bb&!~tl”,” i n t h e v i c i n i t y of 570 cm-l and
I_
as observed and he made a de o f t h i s . In t h
were taken as s
s . The a b s o r p t i o n was a t 670 and 58
t h e s e l e v e l s , a s h i f t t o hidher wavelengths t h a n Waldron’s
t h e d i f f e r e n c e i n wavelength fbeing 100 cm-l and 200 crn-l,
Regardless o f t h i s , however, it i s b e l i e v e d t h a t both o f t h e s e
t y p i c a l examples demcmstrating t h a t i n f r a r e d s p e c t r o -
group oxldes i s p o s s i b l e .
I

4.5 /The SDectra o f Mixtures of Ferrous

I
~

I Oxid#, Manganese Oxide, S i l i c o n Dioxide,

C h r o ~ u mOxide, and Alumina

i t u t e t h e primary
1 and are t h e
c t s o f a n a l y s i s . Ferrous
anese oxide may well b e
e i n g o f t h e sodium c h l o r i d e
found t h a t t h e i r c h a r a c t e r -
n c l o s e l y resembles t h a t o f
i d e and a-alumina

30
rrendum group ,
s i n the character-
e s e compounds were -i
dioxide formed c r y s t a l - I
dependent o f t h e o t h e r
up o f f i v e oxides.
!
t The f o l l o w i n g d i s c u s s i o n p e r t a i n s t o
i Wave number, an-I
ch were made i n t o
f infrared spectra t o
’
:
es o f t h e s e components
d together. Figure 5
absorption s p e c t r a f o r a
ade up o f t h e s e f i v e
i t i e s with a t o t a l

1
Extremely i n t e r e s t i n g s p e c t r a obtained. The following examples
_are given w i t h r e s p e c t t o t h e q u e s t f differentiability.
45
1. S i l i c o n d i o x i d e could be nguished from t h e o t h e r components

1
u i t e e a s i l y , because i t s a b s o r p t i o ctrum i s independent of t h e o t h e r s .

2 . I t is d i f f i c u l t t o disting between f e r r o u s oxide and

50 anganese oxide because t h e p o s i t i h e i r c h a r a c t e r i s t i c absorption i s
--:I _. __I_-__ I-

L 1 -__
Even Roman odd
 ,: - v i r t u a l l y i__d-__
- -

entical.
--
I
-
__

c
I
I -manganese oxide on
by i t s r e l a t i v e l y c l e a

4. Alumina can very e a s i l y a f d e c t t h e '1055

abso*tion o f t h e o t h e r components.

5. Accordingly, it i s b e l i e v e d t h a t
!i e.s-
only p i l i c o n d i o x i d e can be i s o l a t e d i n a
1
-
s
mixt e c o n t a i n i n g t h e s e f i v e d i f f e r e n t
oxidep and analyzed q u a n t i t a t i v e l y .
*
\

. l5 SO.3- IIt s h o u l d be n o t e d t h a t t h e mixture

examined h e r e c o n t a i n e d equal
of a l l o f t h e components. Since
practice, the included quantities
e.1 8.
it i s b e l i e v e d t h a t t h i i
20
1 I I I I I
would b e a p p l i c a b l e t o broad s t u d i e s
0.1 0.2 0.3 a4 0.5 0.6 methods can b e
SiOI, ms

:-Figure 7 . C a l i b r a t i o n
25 k u r v e s of S i l i c o n Dioxide. a r e based on t h e s t u d y
properties of silicon
'
1
( A ) S y t k 8bolptidd at lOWa-1,
*
11mCm-'i
(B)
( a ) th!!wh
~b!
8I
- m a r e r l a l wm a r e
mea-: potassium bromide d i s k
was t a k e n by mixing t h e
t a r f o r t h e time n e c e s m
t o assure uniformity. Figure 7 e n t curve o b t a i n e d u s i n g t h e
a s e l i n e method. I t i s apparen n e a r i t y was o b t a i n e d .

E. Conclusions
35
- S t u d i e s were made of t h e i n f r a r e
-such as aluminum, calcium, e t c . I t has
d been
-c o r r e l a t i o n between t h e c h a r a c t e r i s t i c
-formation o f t h e s e s u b s t a n c e s . Finall{
40 -method t o a n a l y t i c a l chemistry were p r e
-similar fragmentary r e p o r t s concerning
-o x i d e s , b u t no i n t e g r a t e d s t u d i e s have
-d a t a p r e s e n t e d h e r e a s a f o u n d a t i o n f o
-chemical and physico-chemical s t u d i e s o
a b s o r p t i o n s p e c t r a of metal oxides
p o i n t e d - o u t t h a t t h e r e i s some
b s o r p t i o n and t h e c r y s t a l l i n e
examples of t h e a p p l i c a t i o n of t h i s
e n t e d and d i s c u s s e d . There have been
he i n f r a r e d a b s o r p t i o n s p e c t r a o f
been found. I t i s planned t o use t h e
subsequent, d e t a i l e d a n a l y t i c a l
t h i s subject.

45 k In c o n c l u s i o n , warmest thanks
Co. L t d . , Tokyo Research I n s t
uidance and encouragement during t h
M r . T o s h i j i Matsuhira of t h e Naga P 1
t h e extreme i n f r a r e d
xtended t o t h e Chief of t h e Yawata
D r . S a n i c h i r o Mizukawa, f o r h i s
r s e of t h e p r e s e n t s t u d y , and t o
f t h e H i t a c h i Manufacturing Co. Ltd.,
t i o n spectrum measurements.

I__. 9
Even Roman odd
 - ---- __-__-~----___-- ___
i--- - 1
L
1
-1
I
L 1
5 t o , I c h i o ; Toda, Junnosuke; nd Yukio Morimoto: " I n f r a r e d
o r p t i o n Spectra", C@Ha?dfl k $ t l $ 4 (Kagaku No R y o i k i Zoh
[Special I s s u e on Chemistry] 544(B 55, 1963, (Nankodo).
. Miller, F . A. and C. H. Wilkins, V a l . Chem. 24, p . 1253, 1952.
10
. Hunt, J . M . ; Wisherd, M. P. and L . ' C . Bonham, i b i d . ; Vol. 2 2 , p . 1478,
1950.

15

Saksena, B. D. and S. Viswanathan; i b i d . , Vol. 69B, p. 129, 1956.

1. Willmott, J . C . ; i b i d , V o l ~ ~ ~ , ~ ~ , ~ 3 ~ . , , ~ ~ 5 0 .
20 Gross, E. F . and B. A. Karryev; DoE?l. Akad, Nauk SSSR, Vol. 84, p. 261,
1952.
Johnston, R . W. and D. C . Cronemeym; Phys. Rev., Vol. 93, p . 634, 1954.

t
Matsutaka, Amane; K i n z o k u s h i [MetaIs Journ 11, Vol. 28, p . 615, 1964.
Terada, Makoto; and Tatsuo Maekawa, I b i d , 01. 29, p. 421, 1965.
25 Mizushima, S. and K . Sato; S i t e d b). I . Nak gay$rr$The U n i v e r s i t y o f
- m.---- ----
Kiriyama, Zoichi ; and Hideko Kiriyz.ma; "St c t u r a l Inorganic Chemistry,"
Vol. 1, p. 125, Kyoritsu Press, 1964.
1 8 . M i t s u i s h i , A. and H. Yoshinaga; J . Phys. SOC. Japan, Vol. 13, p. 1236,
30
1958.
t l 9 . Waldron, R . D . ; Phys. Rev., Vol. 99, p . 1727, 1955.

35 r a n s l a t e d f o r t h e National and Space Administration under

o n t r a c t No. NASw-1695 by o r a t i o n , PO Box 729, Glen Burnie,
d . 21061.
. .
40 -

45 ~

50
1

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