The infrared absorption spectra of 12 kinds of metal carbides, 11 kinds of nitrides, and 7 kinds of sulfides, a total of 30 materials, were measured and the application of the infrared spectra of these materials to analytical chemistry was discussed. The measurements were done in the frequency (wave length) range of (1400 to 400/cm (7 to 25 mu). The carbides Al4C3, B4C, the nitrides AlN, BN, Si3N4, WB, and the sulfides Al2S3, FeS2, MnS, NiS and PbS were noted to have specific absorptions in the measured region. The sensitivity of Boron nitride was especially good and could be detected at 2 to 3 micrograms in 300 mg of potassium bromide

Kammori, O.

Kurosawa, F.

Sato, K.

English

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oNASA TECHNICAL MEMORANDUM
 NASA TM~ 75900
INFRARED ABSORPTION SPECTRA OF METAL CARBIDES, NITRIDES
AND SULFIDES
0. Kammori, K. Sato and F. Kurosawa
Translation of "Kinzoku Tankabutsu, Chikkabutsu oyobi Ryukabutsu
no Sekigai Kyushu Supekutoru," Japan Analyst, Vol. 17(1968)
pp. 1270-1273
(MASA-Tfl-75900) INFHAfiED AiJSOBPTION SPECTRA N81-19249
OF METAL CARBIDES, NITRIDES AflD SULFIDES
{National Aeronautics and Space
Administration) 10 p HC A02/MF AO1 CSC1 07D Unclas
G3/25 41762
NATIONAL AERONAUTICS AND SPACE ADMINISTRATION
WASHINGTON, D.C. 205^6 FEBRUARY 1981
https://ntrs.nasa.gov/search.jsp?R=19810010722 2020-03-21T13:34:01+00:00Z
STANDAHD TITLE PAGE
N A S A TM 75900
4. Ti t le and S u b t i t l a * INFRARED ABSORPTION SPECTRA
3F METAL CARBIDES, NITRIDES AND SULFIDES
7. Author! s) 0. Kammori, K. Sato and
F. Kurosawa
9. Per forming Orgoniiotion Norn* and Address
Leo Kanner Associates
Redwood City, California 9^063
12. Sponsoring Agency Norn* ond Address
National Aeronautics and Space
Administration, Washington, D. C . 2t)546
,
S
-^ru0a'ry 1981
•6. PerForming Orgoniiolion Coda
8. Performing Orgonuolion Report No.
10. Work Unit No.
NASw-3199
13. Type of Report and Period Covered
Translation
14. Sponsoring Agency Code
is. Supplementary Notes Translation of "Kinzoku Tankabutsu, Chikkabutsu
oyobi Ryukabutsu no Sekigai Kyushu Supekutoru," Japan
Analyst, Vol. 17. (1968) pp. 1270-1273-
16. Ab.troct
 The lnfrared absorption spectra of 12 kinds of metal
:arbides, 11 kinds of nitrides and 7 kinds of sulfides, a
total of 30 materials, were measured and the application of
the infrared spectra of these materials to analytical
chemistry was discussed. The measurements were done in the
frequency (wave length) range of (1400 - 400 cm~1(7 - 25y).
The carbides AljjCo, BijC, the nitrides A1N, BN, Si3N|j, WB,
and the sulfides A12S3, FeS2, MnS, NiS and PbS were noted
to have specific absorptions in the measured region. The
sensitivity of Boron nitride was especially good and could
be -detected at 2 - 3VS in 300 mg of potassium bromide.
17. Key Words (Selected by Author(s))
19. Security Clossif. (of this report)
Unclassified
18. Distribution Statement
Unlimited-unclassified
20. Security Clossif. (of this poge) 21. No. of Pages 22. Price
unclassfied
NASA-HQ
INFRARED ABSORPTION SPECTRA OP METAL CARBIDES, NITRIDES AND SULFIDES
0. Kammori, K. Sato, and F. Kurosawa
Tokyo Research Institute, Yawata Iron and Steel Co., Ltd.,
Ida, Kawasakishi, Kanagawa-Ken
The infrared absorption spectra of 12 kinds of metal /1270*
carbides, 11 kinds of nitrides and 7 kinds of sulfides,
a total of 30 materials, were measured and the application
of the infrared spectra of these materials to analytical
chemistry was deiscussed. The measurments were done in
the frequency (wave length) range of (lMOO-400 cm~l
(7-25y). The carbides All^, BijC, nitrides A1N, BN,
SioNij, WB, and the sulfides A12S3, FeS2, MnS, NiS and
PbS were noted to have specific absorptions in the
measured region. The sensitivity of Boron nitride was
especially good and could be detected at 2-3yg in 300
mg of potassium bormide.
1. Introduction
Interposed material and effluents in steel plan an exceedingly
important role. At the present time many attempts are being made
to explain the behavior of these materials by extracting, separating
and measuring them. Recently, in addition to the usual electrolytic
and wet methods, other methods such as the machine analytic method,
derivatography, X-ray diffraction, electron beam diffraction, and
X-ray micro analyser (EPMA) have come into wide use. However, all of
these methods have their merits and short comings and none of them
are definitive. Therefore, we thought it would be interesting to
apply the infrared absorption method which has been very little used
for inorganic analysis.
The infrared absorption method has the advantages of a) the sample
can be less than 1 mg, b) there is no reaction or dissolution as in
derivatography and c) detection can be made even in non-crystalline
material. If used with proper samples, good results should be expected,
though not important reports have appeared thus far. There is almost
it
Numbers in the margins indicate pagination in the foreign text.
no accumulation of information concerning the absorption and spectra
of the inorganic materials of this report, though part of them
appeared in Ramdas report [1].
The authors are doing research on the application of infrared
spectra to the analysis of steel [2-6], and this report continues
from our report on oxides [2]. Here we investigate the absorption
spectra of carbides, nitrides and sulfides.
2. Experiments
2.1. Measurement
A Perkin-Elmer 521 model diffraction grating spectrophotometer
was used. The experiments were done by the potassium bromide disk
method. The 1 mg samples (20 yg in the case of BN) were weighed /1271
out with microscales and mixed with 300 mg of.potassium bromide powder.
After this was uniformly mixed in an agate mortar, disks of 13 nrni
diameter and 1 mm thickness were prepared in a disk molding vessel.
The area of measurement was 1400-400 cm (7-25 y).
2.2 The Samples.
The 12 carbide samples are shown in Table I, the 11 nitride
samples in Table II, and the 7 sulfide samples in Table III.
3. Experimental Results and Discussion
Of the 12 kinds of carbides two, A1.C , and B^C were noted to
have specific absorption in the frequency area measured. Of the 11
kinds of nitrides, four, A1N, BN, Si N, (a-Si N. and B-Si N,), and
WN, were noted to have specific absorption in the frequency area
measured. Of the 7 kinds of car sulfides, five, Al S , PeS , B-iyinS,
MiS and PbS were noted to have specific absorption in the frequency
area measured. Figures 1-3 show the absorption spectra with.the
absorption positions. Below we will discuss the relationship between
the absorption spectra and the structure of these materials.
TABLE I METAL CARBIDE SAMPLES
TMilr: I Metal carbide samples
Sample X My diffradion
| Miiniintini carbiitf, AliCj AM-i •
J)..T..n carbide, B.C n«r-f
1 Chr..m"!in rarlii.lr. Cr,C] IOir-A
i ir.fmu,,, r.-..i,i.i,-. MIC "if:
j Molybdenum rarbiflr. Mo,C Mn,U
ft ,\ir,liium railjidr. MiC M'C
7 Nirtrl rarhidf. NiC NiC
R lanialuin raitmlr.. TaC TaC
y Tiljuinm rnrhidr. TiC 1'^
10 \-ai,.vliuin eatl.idf, VC VC
|| Tiuig«.n caibidc, WC wf:
12 Zirmnium raibidr, ZiC 7-^
t Involici sraphitc; tt Involve unknown mafrial
TABLE II METAL NITRIDE SAMPLES
Table II Ntelal nitride samples
No.
1
2
J
4
i
6
7
8
9
10
II
Samplr.
Aluminum nitridt
Boron nilrirle, B\
Chromium nilridc, C.T|N(CiN)
Hafnium nitride, HFN
Niobium nitride^ NbN
Silicon nitride. SijNi
Tantalum nitride
Titanium nitride, TiN
Vanadium nitride, VN
TunRMen nitride
Zirconium nitride, ZrN
X-rav
AIN
B.N
J-Cr,X,
HfX(llfO
.NbN(Nb>
.-SijN,,
TaNtt
TIN
VN
0-WN(W
ZrN
ilidraclion
CrN(O)t
I, I'Ot
IO, (NbN)IHrt
J.Si,X,
, «'0,)t
t Minor component*; tt Unknown material is involved.
TABLE III METAL SULPIDE SAMPLES
Table III Metal sulphide samples
No.
1
1
3
4
•i
«
1
Sample
Aluminum *ulpht<)r, AIS
Cuprous sulphide .
Frrrom «nlfinV
 ( FrS
rvritr, FrS,
.Mnn«.im r^ mlplildr, MnS
Nirkrl tutfiric
Lrad ^ulpliirir
X-ray diflVaclinn
AI,Sj(AI,c(c.)t
CuS.<Cu,S(CuS)»»
FeS(«-Fr)tt
FrS(FrS,,Fr,0,)»»
f MnS»»t
Amorphous
PI)S
* Many trnptiritlen are InvnhiM ; t* Minor
tt* L'»kiiown malmali trr im-nlvrrl.
ORIGINAL PAGE IS
OF POOR QUALITY
.= lOOi
1400 12UO 1000 800 600 400
H'ave numbefp cm"'
Fig. I Infrared absorption spectra of metal carbides
100
- AIN
100
b 0
I 100
0
100
819
494 M30
640
780
1400 1200 1000 600 600 400
U'ave numhrr. rnr'
Fig. 2 Infrared absorption spectra of metal nitrides
3.1 Carbides
The crystalline structure
the carbides [?] were in general
of the interstitial type, as for
example, HfC, NbC and TaC . Most
of the carbides tended to become
/12?2
berthollide. was similar to
salt and Cr C2, NIC and WC each had
their peculiar structure. Only two
kinds of carbide were noted to have
specific absorbency and it is
supposed that the others have
absorption bands in the far infrared
region. Consequently, it would be
difficult to attempt a study with
only these results.
From the analytic point of view,
B,C had. a specific absorbency of
1085 cm"1. The authors have already
used this for separative measurement
of boron effluents in steel obtaining
a calibration curve of fairly good
linearity [5,6].
3. 2 Nitrides
The crystalline structure of the nitrides [?] was mostly of the
NaCl type as seen in HfN, NbN and TiN. Consequently, these materials
had only one absorbency, Since the absorption band was not inside
the area measured, it was assumed that it was in the low frequency
far infrared section below 400 cm" .
100
. AI.S:
0
100
0
JOO
-670
1085
,3-MnS
.1130
100,
0
100
- I'bS
1-100 600 4001200 1000 eoo
\\'a\'c number, cm'*
Fij. 3 Infrared absorption spccira of
mrtal sulphides
-1
A1N belongs to the wurtzite
type, and is known as a material that
plays an important role in certain
kinds of steel, such as IN steel.
BN was of hexagonal layered graphite-
like structure and diamond-like
zinc-blende type. Boron is known
as a material that enhances the
quenching qualities of steel [8],
and is .beginning to be used in
metallurgical research and recently
in research by the analysis of state
method [5, 6, 9]. BN had specific
absorption at 1383 cm and 819 cm"
The 1383 cm" absorption band was noted
to be very strong. The absorbency
was about 0.1 under the measuring
conditions of our experiment with a
M yg sample. Since detection is
sufficient at under 1 yg, this can
be applied to the separation
analysis of steel which contains boron.
Si N^ was of a-type and B-type.
Consequently, there is no clear specific individual adsorption in the
absorption spectrum of figure 2. This material is of group IV elements
and this nitride is known as one of the few compounds that satisfy
the valence law. X-ray diffraction showed that the g-WN contained
WO and the origin of the absorption band in figure 2 is not known.
This could be resolved if the absorption spectrum of WO were known.
Since only 4 of the nitrides were noted to have specific absorption,
the relevance of the absorption spectra to the structure cannot be
determined.
3.3 Sulfldes
There is a fair amount of diversity in the crystalline structures
of sulfides [?]. A defect is that it is very difficult to obtain a
pure material. However, of the seven samples specific absorption
was noted for five.
AlpS was multiform and there was a 3. r ^  g mutual transition.
Its absorption spectrum was broad and the position of absorption
unclear. The FeS? sample contained PeS and Fe_Cv . There was no
absorption band for FeS and since that of Fe_0. is in the vicinity
—1 —1
of 580 cm and 380 cm [2, 10], it is assumed that the absorption
band in figure 3 is mostly that of FeS ,
3-MnS, NIS NiS and PbS absorption spectra were very interesting
.for their very great similarity. However, according to the results
of X-ray diffraction, the g-MnS contained impurities and the NiS
was noncrystalline . Therefore, these materials must be studied
further using other analytical methods.
^ . Conclusion
Compared with oxides, there were very vew carbides, nitrides and
sulfides which had specific absorptions in the measured region.
(liJOO-JJOO cm ). Of the 30 samples measured, specific absorption
was noted in only 11 types, and of these, 5 were sulfides. Almost
none of the materials of the experiment having absorption bands /1273
outside the measured region had absorptions at high frequencies above
1^00 cm . Most of them had absorption bands in the low frequency
far infrared section below 400 cm~ .
Concerning the crystalline structure, HfC is typical of the
carbides and is of the interstitial type. TIN is typical of the
nitrides and is of the NaCl.type. The nitrides were prone to become
berthollide. The sulfides all had their peculiar structures which
were diverse. No tendency for linearity between the crystal structure
and absorption spectra was noted. However the absorption spectra of
these materials can be very useful in the qualitative identification
of compounds and can be effective in everyday analysis. BN, especially,
can be detected when t he quantity is 1/100. In this experiment,
M yg of BN in 300 mg of KBr gave absorbence of 0.1, which is very
sensitive. It is possible to use BN in the quantitative analysis
of actual samples.
It is exptected that more interesting information can be obtained
concerning these inorganic materials by a study of their infrared
absorption in the far infrared section.
In conclusion, we would like to thank Dr. Mizushima, Head of
the Tokyo Research Institute of this Company for his guidance and
encouragement.
REFERENCES
1. Ramdas, A.K, Proc. Indian Acad. Sci., 37A 571 (1953).
2. Kammori, 0., N. Yamaguchi and K. Sato, Japan Analyst 16 1050 (1967).
3. Sato, K., F. Kurosawa, N. Yamaguchi and 0. Kammori, Koka 71 208
(1968).
4. Sato, K., N. Yamaguchi and 0. Kammori, Japan Analyst 17 208 (1968).
5. Kammori, 0., Y. Taguchi and K. Sato, Kinzokushi [Journal of Metals]
3! 634 (1968).
6. Kammori, 0., Y. Yamguchi, K. Sato and F. Kurowawa, Ibid 32 779
(1968).
7. Kiriyama, R., and H. Kiriyama, Koso Muki Kagaku [Structural Inorganic
Chemistry] 1, Kyorltsu PuDllsning"Co., 1964, pp. 171, 193, 206.
8. Takao, Z., Japan Analyst 16^ 1104 (1967).
9. Abe, Y. and Yamada, Tekko [Iron and Steel] 53. 553 (1967).
10. Waldron, R.D., Phys. Rev. 99. 1727 (1955).


Infrared absorption spectra of metal carbides, nitrides and sulfides

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