Powder Technology.

18 (1977) 45 - 48
@ Elsevier Sequoia S.A., Lausanne - Printed in the Netherlands

Specific

Surface Area hfeasurements

on Ceramic

45

Powders*

E. S. PALIK
General

Eiectric

Company.

(Received February

1099

Iumhoe

Road.

Cleweland.

SUMMARY
Surface area measurements on ceramic
powders are determined by gas adsorption
using the Brunauer-Emmett-Teller
(B-E-T_)
equation. Two methods are described: the
static and the dynamic. Emphasis is placed on
sample preparation prior to adsorption_ Data
are presented which compare the two methods
along with the results of a round robin study
on surface area measurements on an alumina
sample_
In this communication
the BrunauerEmmett-Teller
(B.E.T.)
method of surface
area measurement will be briefly reviewed,
some remarks given on the importance of
surface area data to the ceramics industry,
some comparison data by static and continuous flow methods presented, and finally a
preliminary report issued on an ASTM surface
area round robin _
Briefly, in the static method of surface area
measurement,
the amount of adsorbed gas is
usually determined by measuring pressure
differences in a calibrated high-vacuum apparatus. In the dynamic or continuous flow
method, the amount of adsorbed gas is determined by concentration
measurements
utilizing a thermal conductivity
detector_
The B.E.T. principle is embodied in the
well-known equation:
P
Y(P,

-P)

1
=-+
v,c

(C-Up
v,c

PO

where P = equilibrium pressure of the gas,

P,, = saturation pressure of the gas at liquid
Na temperature,
V = volume of gas adsorbed
*Paper presented at the 8th Annual Meeting of the
Particle Society Conference, Chicago, August,
1976.

Fine

OH

111

IO (USA.)

15. 1977)

at equilibrium pressure, Vm = volume of gas

required to form a monolayer,
and C =
constant related zo a special value of the heat
of adsorption:
C=esp

HI -Hz
RT

where H, = heat of adsorption at the monolayer point, and HZ = heat of condensation.

This equation should result in a linear plot
of P[V(P,
-P)
against P/PO and the value of
V, can then be calculated from the slope and
intercept_ The equation is capable of describing type 1, type 2 and type 3 isotherms depending on the C constant_ In general, it has
been found that only type 2 isotherms (i.e.
those with high C values) have well-defined
knee-bends,
which are essential for accurate
V, values. For type 2 isotherms, the B_E.T.
equation has been found to be valid generally
between 0.05 and 0.3 relative pressure. The
internal consistency of the equation has been
demonstrated
by many measurements on
several solids, and the degree of correspondence between the specific surfaces obtained
with several adsorbates allows confidence to
be placed in the method_
Having obtained the value of V, from the
B-E-T_ plot, the following equation is employed to calculate SW., the specific surface
area in m*/g for the sample:
S,&. = Nav,
M,M
where SW = specific surface area in m*/g,
N = Avogadros
number, 6.023 X 10 molecules/gram molecule, u = area occupied by
one adsorbate molecule, 16.2 X 10p20 m* for
N2, 19.5 X lo- 20 m2 for Kr, V, = monolayer
capacity in ml, M, = gram molecular volume =
22410 ml, and W = sample size in grams.

The analysis time can be considerably

shortened by using a one-point adsorption
method, particularly if a dynamic system is
used, provided the C value of the sample is
Iarge (>50).
Most materials which eshibit a
tvpe 2 adsorption isotherm with nitrogen have
high C values and, therefore, present no problem with one-point adsorption_ The error in
most cases is less than 5% if C = 50 at a relative pressure of O-3.
First, some words on the importance of
surface area data to the ceramic industryTable 1 lists some of the properties of pow-

ders which can be affected by the estent of

TABLE

Effect

of temperature

Temp_

("C)

3%
403
506
607

T-ABLE

I_
2.
3.
4.
5.
6.
S_
S_
9_
10.
11_
1%.
13.
L-I.
15.
16.
Ii_
18.
19.
20.

of surface

area on

powder properties

50-Z
SO7
905

Blending
of particles
Adherence
of particles
Hiding or covering
power of paints
Flow of particles - bulk density
Pa&kg
of partictes (escape of gases)
RheoIogical
properties
(yield value: spherical
<
acicular 4 lamellar)
Sedimentation
Flooding
Floccuhtion
and dispersion
Drying
Optical properties
Burning rates of propeIlants
and solid fuels
(primer)
Dinolving
rates of chemicak
Weatherability
of paints
Leaching
rate and extraction
efficiency
of ores
Quality
of concrete
aggreg&tes
Minerals separation
by flotation
Soil bearing strength
Reinforcement
of plastics
Strength
factor in particle board manufacture

Prior to gas adsorption. it is essential that

the sample surface be degassed, cleaned or
otherwise freed from adsorbed gases by either
elevated temperature vacuum bake-out or
elevated temperature flushing of the sample
with an inert gas for periods of up ro 24 hours
depending on the sample requirements and

0.65
0.32
S.S.A.
(mlg)
DL bake-out
temp.

Sample

previous thermal history of the sample. For

example, a knowledge of the thermal history
of the sample will indicate what bake-out
cond:tions to employ. A consideration of the
thermal stability of the sample also will dictate bake-out temperatures_ Co,O, is an
esample as shown in Table 2_

of

300

COJO/&
cog04

1
B
3

32.5
3-1-T

29.4
21-O

47.0

co304

62.1

3i.i
35.1

X~TIFW4i

Fig.

Co304

0-i

1057

co,o,

Sample:

S.S.A. (m*/g)

100

iuflueuce

area.

50
32
22
8.6
2.0

the surface area_

The

on surface

l_ hlultipoint

(ST?.iIC>~25

vs. single-point

B-E-T_

It is essential that the thermal history be

known or proper bake-out conditions be
utilized to prepare the sample for adsorption
if the surface area data are to be meaningful.
Before discussing multipoint static and
single point dynamic B-E-T_ data, the two
methods should be compared. In our laboratory both instruments are employed,
static
and dynamic, and Fig. 1 shows a correlation
plot involving a variety of samples (A120a,

_
_
__

_
,?l
c-_

41

TiO,, 5X0,). The correlation coefficient

for
the dozen or so analyses involved is 0.99. The
range of surface areas is 0.6 - 270 m/g_ With
such a correlation, it is possible to utilize the
one-point continuous flow method for nearly
all of the samples and thereby save considerable analysis time.
An in-house standard surface area sample
is used in our Iaboratory, consisting of a wellcharacterized titanium dioside powder.
Table 3 summarizes some of our TiOs surface
area data.
The main thrust of this paper will be to
present data from a round robin carried on
by ASTlM subcommittee
C21.07.
In this work,
eight different Iaboratories participated, and
a variety of commercial
instruments were

TABLE
Static

3
us. dynamic

Static
Dynamic
Xccepted

TABLE
Sample:

employed
(the round robin study is still in
progress). It would be appropriate to present
the first phase of the work at this time, which
is summarized in Table 4. The mean and
standard deviation are identical for both single
and multipoint data, 1.06 2 0.1 m*/g.
It is evident after examining these data that
once the sample has been pretreated (in the
case of the alumina, pre-firing at 1000 C for
-5 minutes to convert to the e-form),
the
specific surface area obtained is essentially
independent of which laboratory performs
the analysis on which instrument under which
bake-out conditions,
which adsorbate is used
and whether single or multipoint data are
used. In other words, surface area measurement
is a straightforward
determination,
not subject
to the usual types of errors encountered in
physical measurements.
All this is, of course,
true thus far only for alumina powder which
with nitrogen eshibits a high C value (>50).
For a given sample, knowing the thermal
history or controlling bake-out conditions
and establishing the magnitude of the C value,
a method can be developed to determine
specific surface using any of the many avail-

B.E.T.

data

for TiO2

standard

10.6 + 0.3 m2/g

9.5 * 0.7 m2/g
10.3 m*fg
(mean value of 6 tabs)

value

1
X120,

Laboratory

(pretreated).
Instrument

B.E.T.

round

Outgassing
Temp.

robin

(C)

conditions
Time

Xdsorbate

Surface

(h)

area (mlg)

Single

Multipoint

1.13
_

b1*2100D

145

17

Kr

1112300
h12205

150
150
150

17
0.67
0.67

Kr
N2
Xl-

0.96.
0.97,

Strohlein
Shell-Sorpt**

25
150
200

16
1
2

N,
N2

_
1.08,
1.07
1.18,1.1-l

bI*MIC-103
Quantasorb***
Monosorb***
hlonosorb
Monosorb

125
150
150
150
150

17
1
1
1
1

Nq
N2
N
N2

1.03,
1.05.
l-OS,

N2

1.07,1.06

hI*2100D
M2100D
Monosorb

150
150
150

1
16
1

Kr
Kr
N2

150
150

1
1

N2

I-I

Quantasorb
Quantasorb

_
1.09,
1.11
1.05,
1.07
1_01,1_03

N2

B
C

D
E
F

Mean
*Micromeritica
**Perkin-Elmer
***Quantachrome

In&r.
Corp.

Corp.

and std.

1.13

dev.

= 1.06

1.03
0.96

1.0-l
1.04
1.10

* 0.1

1.15.1.13

_
o.ss
1.01,
-

1.05

1.11
1.0-l
1.00.1.02
1.05,
l-02
1.03

48

able instruments found today that will yield

reproducible
and comparable values.
The above round robin study is being estended to silica and other ultra-fine forms of
alumina powders and will be reported at a
later date.
It is concluded from this work that for
samples having a known thermal history, a

high C value, and a surface area >0_5 m*/g,

one can use N, single-point adsorption_ For
low surface areas (<O-5 m*/g) and low C
values (<50),
mu!tipoint adsorption measurements using krypton will result in better data,
krypton being preferred because of its higher
boiling point compared with nitrogen
(-152
C against -196
C)_