Beruflich Dokumente
Kultur Dokumente
of vacuum
materials-II
Part II of this two part account examines the methods available for the measurement of
outgassing rate. It recounts the results obtained for some selected materials and in particular
examines methods for reducing the outgassing rates of materials for use in ultrahigh vacuum.
Finally it presents outgassing rates for various materials in tabulated form.
1. Introduction
ptorr
Time,
347
steel 5 x lo-
cllo stainless
steel 1.0.
torr 1. s-l
cm-
where R is the universal gas constant; T is the absolute temperature; M is the molecular weight of the gas; r is the radius of the
tube; I is the length of the tube in cgs units.
The Rutherford Laboratory apparatus uses an orifice plate
having a circular hole (of approx. 3 mm dia) with chamfered
edges. The plate was sealed between flanges with indium wire.
The whole apparatus was constructed of stainless steel. The
conductance was 1.O 1. s- calculated from the formula.
A
C=.-..-
1000 J(
3. Methods of measurement
3.1 Throughput method. The throughput method attributed to
Zabel has attained considerable popularity. The results obtained by this method are the ones most relevant to continuously pumped vacuum systems. Essentially a sample of the
material to be studied is placed in a vessel which is connected
by a tube or orifice of known conductance to a high vacuum
pump. A vacuum gauge, usually an ionization gauge but sometimes a residual gas analyser, is connected to the vessel containing the sample. The vessel is pre-evacuated, the time noted and
the high vacuum pump started. When it is judged that the
pressure is low enough the vacuum gauge is switched on and
the chart recorder, if used, started. Alternatively to the use of a
chart recorder, pressure readings are taken at intervals which
are short at first but are longer as the rate of reduction of
pressure becomes slower.
Figure 2 shows the apparatus used by Zabel to measure the
outgassing rates of waxes and sealing compounds and Figure 3
the apparatus used at the Rutherford Laboratory to determine
the outgassing rates of glass fibre expoxy laminates.s3 In the
Zabel apparatus the sample chamber was connected to the
pump by a small bore tube of conductance 0.042 1. s-l for air
calculated from the Knudsen formula for a long tube viz. :
c=-
1
1000 J(
2nRT
4r3
. 311.
M >
s-l
l.s-
>
Q=PS
R J Elsey:
Outgassing
of vacuum
materials-11
I
I
I
s,
I
I
I
I
Sample
C
1 + c/s,
i.e. S, > 50C
s-c
the error in ignoring poutis negligible. This is the case when a
11. s-l orifice is used in conjunction with a 2 in. diffusion pump.
If the conductance is too small in relation to the surface area
of the sample an error could be introduced due to readsorption
of the gases evolved. DaytonI
has examined this relationship
and shows that readsorption becomes negligible when the area
of the pumping orifice is greater than 100 times the product of
the sample surface area and its sticking coefficient for the
evolved gases. He states that in general this condition is met if
the conductance is greater than a few tenths of 1 1. s-l for
several square centimetres of sample area. The apparatus he has
used for measuring the outgassing rates of elastomers and
vacuum waxes and greases is shown in Figure 4.
The sample area was about 100 cm2 and the apparatus made
of glass has a choice of two conductances selected by moving
steel balls with a magnet. The conductances are 0.3 and 1.3
1. s-l. These are sample to equivalent pumping areas of
4000: 1 and 900: 1. Dayton claims that for many materials there
is no evidence of readsorption even with the smaller of these
conductances.
Another source of error in outgassing measurements is the
ionization gauge. The effect of gauge pumping and outgassing
from the gauge has been investigated by Moraw.14 A diagram
of his apparatus is shown in Figure 5. The conductance could
be switched between values of 0.09 and 1.5 1. s-l. The sample
vessel could be replaced with a needle valve so that pure gases
Hz, CO, O2 could be introduced and the effects on the two
ionization gauges and the reisidual gas analyser noted. The
difference of the peak heights obtained with the RGA before
and after switching off the gauges was used to determine the
true outgassing rate, by means of a computer programme. It
was found that the ionization gauges (Balzers type IM 15) had
a pumping speed for hydrogen of 0.12 1. s- I, and zero for
other gases when employing a thoriated iridium filament operVG-IA
,8mm
I.!3,8Omm
%kXri.
15mml
b-q
PI
IIIY
L__,_
VI
s
--r--
Pump
III!
69
____----_____
SampA
Trap+&&
349
R J Elsey:
Outgassing
of vacuum
materials-II
Gauge 2
Farvitran
Sample
Farvitron
Chambe;
Ij
:I
1 I!
1Ch;2GaUge
To pump
Refrigera+ed
Pumping
Figure 6.
Apparatus
with two
used by Schram.9
tin
used
by Young.
The outgassing rate for 300 series stainless steel baked for 30 h
at 250C (2-3 x IO-l2 torr 1. s- cm-) was in good agreement
with that found by Calder and Lewin (3 x lo- 12) for stainless
steel baked for 25 h at 300C. Young also found very low
outgassing rates for aluminium baked for 15 h at 250C
(4 x lo- l3 torr 1. s- cm-). Moraw has found similar outgassing rates for these metals after a 20 h bake at 100C.
The American Vacuum Society draft standard AVS 9. l-l 964
Reporting of Outgassing Data states:
4.4.2 Background Outgassing Rate. In those experiments
involving a sample material in a system, the background
outgassing rate must be small relative to the sample outgassing rate. Information substantiating this should be supplied
and may include comparative pressure-time data with the
empty system and with the sample in place.
3.2 Throughput method with variable conductance. By using a
variable conductance in the throughput method in a similar
way to that described by 0atley18 for the measurement of
pumping speed, it is possible to retain the accuracy of the small
fixed conductance but with a much larger conductance. Thus
the conditions of measurement more closely approach those of
an actual vacuum system. This is the method described in
Henry.8a Referring to Figures 9 and 10
1
_,
s-s,
T----i
I
-----_--------
Apparatus
valve
group
sample chambers
Ti Sublimator
baffle
Figure 8.
Gate
Then
Q=
S.P,
Pl
= &P,
25
and
l- ---l
R J Elsey: Outgassing
Figure 9. Apparatus
Oatley method.
of vacuum materials-ii
to determine
Q by
Q.
rate =
R J Elsey: Outgassing
of vacuum
materials-4
same setting. The reading on the recorder then decayed exponentially. After the reading had decayed to 10% of its
original reading the leak valve was closed. The peak partial
pressure and the exponential decay time constant were then
determined from the recording and the various parameters of
the system. If G is the outgassing rate of the surfaces in the
test vessel (see Figure 15):
Vz is the volume of the test vessel;
pz is the pressure in the vessel;
S1 is the pumping speed at the leak valve;
p, is the pressure at the mass spectrometer;
S, is the pumping speed at the mass spectrometer
si 9 sz.
(1)
2
s2
P2
s1
(2)
of vacuum materials-II
R J Elsey: Outgassing
Hugh vacuum
rate of
-L .iquid
Coukter
Thermostot
electrode
liquid
These tests were carried out to find suitable materials for the
construction
of a pressure modulated radiometer for the
Nimbus F satellite. Such a radiometer is a sealed vessel of
150 cm3 volume containing CO2 at about 1 torr pressure. After
pumping to ultra-high vacuum the vessel is filled to the required
pressure with pure CO2 and crimped off from the pump. It
then is required to have a life of 2 years without significant
contamination
of the gas. With a measured outgassing rate of
the vessel and contents of -lo-g
torr 1. s- it was calculated
that the partial pressure of H2 would rise to lo- torr in 2
years.
0
MS
.pgg
a-8
n
v2
Then
and
G.2
Pl = rS
G = PI&~
-.
The outgassing rate for the stainless steel under these conditions was found to be 5 x lo-
torr 1. s-l cmm2 and for
titanium 3 x lo-l2 torr 1. s-l cmm2. PTFE after air baking
Elsey method.
is not capable
of following
the dynamic
R J Elsey: Outgassing
of vacuum
materials-II
ltY2
20
CONTRCUER
d. Sample
c. Sample
40
60
Hours
80
100 120
Figure 18
lo-9;I-i
4. Outgassing
Exp I4.(Sample
process.(Sample
5 Exp 15)
6 Exp 17)
9 Exp30)
Figure 19
Figures 17-19. Outgassing rates of IS/S/l stainless steel after various
treatments (from Barton and Govier 1970).
d2I
0
20
40
60
80
100 I20
Hours
a.Honed
exposed
sample following
b. Sample exposed
to air 6 vapour
smearing
Figure 17
(Sample
I Exp2)
c. Sample following
degreasing.
354
to air. (Sample
degreased.(Sample
with cutting
I Exp 41
oil 6 vapour
I Exp3)
This was for stainless steel cleaned by glass bead blasting and
baked in air for 61 h at 450C followed by a 15 h vacuum bake
at 250C. To determine if the surface layer of oxide formed a
barrier to the diffusion of gas from the interior of the metal,
Young glass-bead blasted the surface to remove the oxide and
repumped the sample with an additional I5 h vacuum bake at
280C. The same outgassing rate was measured. It would appear
that the baked stainless steel is not recontaminated easily and
once it has been well degassed a low temperature bake is
sufficient. Young found that electro-polished stainless steel
when baked for 30 h in a vacuum at 250C had an outgassing
rate of 2 x IO- l2 torr I. s- 1 cm- after 24 h of room temperature pumping. The same result was found for stainless steel
shot blasted with glass balls. The method of shot blasting with
high velocity glass balls is useful for removing stains and oxide
and leaves a matt finish. Young found no evidence to suggest
that the very smooth surface produced by electro-polishing is
an advantage. For comparison with high temperature baking,
Young vacuum baked a sample of the same stainless steel to
450C for I7 h. After cooling and pumping for 24 h an outgassing rate of 4 X IO- l3 torr 1. s- crnv2 was obtained.
Stainless steel has for many years been considered the best
metal for the construction of vacuum vessels and components.
In contrast, aluminium has been considered a rather poor
metal for this purpose. It has a reputation as a porous gas-filled
materiaLz5 Aluminium has a lower hydrogen solubility than
other common metals, and has a low diffusion coefficient at
room temperature. Aluminium is more difficult to weld than
stainless steel but techniques for producing satisfactory leak
tight welds are available. Vacuum cast aluminium has good
properties for vacuum vessels. Also the electron storage rings
at Stanford SPEAR are constructed of rectangular cross section
tube extruded from aluminium. It is difficult to make bakeable
all-metal leak tight seals between aluminium flanges. This
problem has been solved at Stanford by explosion-bonding
aluminium to stainless steel and making the flanges from this
material. The aluminium part of the sandwich is welded to the
aluminium tube. Young has measured an outgassing rate of
4 x IO-L3 torrI.s-cm-2fortypelIOOaluminiumwhichwas
cleaned with detergent, rinsed in acetone and baked for I5 h
in vacuum at 250C. At Stanford the aluminium vessels are
baked in vacuum ovens before assembly and not baked in situ.
Clean-up is achieved during operation of the electron beam.
6. Vacuum baking of stainless steel
Stainless steel contains large amounts of hydrogen. The
hydrogen dissolves in the metal during manufacture. It was
shown in Part I that after the initial removal of surface
gas the ultimate pressure will be controlled by diffusion from
the bulk. It was also shown that the rate of desorption was
proportional to the initial gas concentration and to the square
root of the diffusion coefficient, i.e.
qt = CoD112 (nt)-2
In stainless steel at room temperature, D is high enough for
diffusion of hydrogen to limit the pressure attainable and yet
low enough to prevent the concentration of the gas in the metal
being significantly depleted in a reasonable time. D varies
exponentially with temperature so to improve the vacuum
either D can be lowered, e.g. drastically by immersing the metal
in liquid heIiumz6 or the gas concentration in the metal can be
355
R J Elsey: Outgassing
of vacuum
materials-II
(Ha stainless
and &co
(H, stainless
t (s)
1.0 x lo6 (11 days)
8.6 x lo4 (24 h)
1.1 x 104(3 h)
3.6 x lo3 (1 h)
3.5
3.8
3.0
9.0
x
x
x
x
T(C)
10-a
10-7
1o-6
1o-6
300
420
570
635
To rotary
Pump
kiIq--=
for investigation
(from Govier and McCracken 1970).
Table 1. Outgassing rates of 300 series stainless steel (from Calder and Lewin)
Specimen A: outgassing rates (torr 1. crnm2 s-l)
Measurement
Specimen preparation
temperature (C)
f 24
Degassed several times-total
45 h at 360C
356
(1.3-=*)
Hz0
CO-N,
CO,
0,
2.5-13
of
i 100
* The superscripts
H2
6.4:
[4.7 - 151
1.9-12
2.2-12
1.,I,,
2.6-12
1.0-l*
6.4-13
8.4-14
3.6-l
9.9-13
[2.6-l
19
1.3-12
2.7-I2
19
19
Table 2. Outgassing rates of 300 series stainless steel (from Calder and Lewinr)
Hz
20
20
20
40
3*9-12*
4.5- r2
W::
100
20
20
20
20
35
53
2.1 -I0
3.0-12
3.0-12
3.0-12
2.8-2
5.6-r2
1.6-
75
20
20
20
47
72
105
145
200
20
20
4.4-11
1.5-12
1.5-12
1.4-12
5.3-12
1.5-11
3.9-l
9.2-
2.5-r
1.1-12
1.2-12
Hz0
CO-N,
02
1.7-14
6.1 -I4
1.9-14
2.0-14
1.5-14
4.7-13
l.SG
-
1.7-2
1.7-14
1.1 -14
(---)
::;I::
5.8-I4
{1.6-r3}
(---)
G:
1
-
r1.G51
6.3 -I4
1.4-13
2.6-l
[4.3-51
CO-N2
02
1
1.0-13
;;\z;;
(---)
;:;I:;
-
w;7
co2
t;.;:::;
1:0-4
3.6-l.+
-
* The superscripts denote the power of ten by which the numbers should be multiplied.
Table 3. Outgassing rates of 300 series stainless steel (from Calder and Lewin)
Hz0
Hz
20
20
20
100
1.3 --14t
(;:,9;:
20
100
200
co2
1.2-14
1
-
(---)
2.1 -I4
[4-61
2.3-r
1.0-14
8.7-ls
1.9-14
(-1)
3.1 -14
R J Elsey: Outgassing
of vacuum materials--II
(b)
Outqassinq0RW
dlschorqain helium.
(0)
10-b Outqassinqafter
no discharge.
IOmin.
SOOrnk u.
(d)
Outqassiq after
disahorqrin arqon.
zsmr 10mn.s00mAAc.
Outqassinqafter
discharp in neon.
lOOST 3Omin soomA*c
[e)Outqossinq oftrr
10-b
dischorqo in orqon.
loom7
SOmin
IOOrnl
IS
R J Elsey: Outgassing
of vacuum
materials-4
Table 4. Metals
K, torr 1. s- cm-*
Material
Aluminium
Aluminium
Aluminium
Aluminium
Aluminium
Aluminium
(fresh)
(degassed 24 h)
(3 h in air)
(fresh)
(anodised-2 pm pores)
(bright rolled)
Duralumin
Brass (wave-guide)
Copper (fresh)
Copper (mech. polished)
OFHC copper (fresh)
OFHC copper (mech. polished)
Gold (wire fresh)
Mild steel
Mild steel (slightly rusty)
Mild steel (chromium plated polished)
Mild steel (aluminium spray coated)
Steel (chromium plated fresh)
Steel (chromium plated polished)
Steel (nickel plated fresh)
Steel (nickel plated)
Steel (chemically nickel plated fresh)
Steel (chemically nickel plated polished)
Steel (descaled)
Molybdenum
Stainless Steel EN58B
Stainless Steel 18/9/l (electro polished)
(vapour degreased)
(diversey cleaned)
Stainless steel
Stainless steel
Stainless steel ICN 472 (fresh)
Stainless steel ICN 472 (sanded)
Stainless Steel NS22S (mech. polished)
Stainless Steel NS22S (electro polished)
Stainless Steel NS22S
Zinc
Titanium
Titanium
1,
63
41.4
66.5
62
2760
1700
4000
400
35
188
19
1580
5400
6000
100
600
70.5
91
42.4
27.6
83
52.2
3070
52
-
=I
1.0
3.2
1.9
1.0
0.9
6.0
3.06
4.75
3.25
322
75
350
100
41.5
3.56
12.6
1.63
5.1
500
130
9.0
100
5.8
8.0
4.94
2.33
7.05
4.6
2950
3.67
14
2
1
3
210
200
14.7
10.4
4.6
4.28
13.5
322
18.4
3.68
0.75
2.0
1.0
1.0
1.3
1.1
2.1
1
3.1
1
0.75
1
1
0.9
1.1
1
1
0.6
1.0
1.1
0.7
0.9
1.2
0.5
1.0
1.3
1.4
0.6
1.0
1750
900
135
82.8
17.1
42.8
144
2210
113
40
x IOr0
El0
1.0
0.9
0.9
0.9
0.9
1
0.75
1.2
1.0
1.0
1.3
1.1
1
1
1
0.75
1
1
0.9
1.1
1
1
0.7
1
1.6
-
0.75
0.75
0.9
0.8
0.7
1.0
1.9
0.8
1.1
1
Ref
9
9
9
9
9
13
13
13
9
9
9
9
9
13
13
13
13
9
9
9
9
9
9
9
9
13
15
15
15
13
13
9
9
9
9
9
9
9
9
Material
Treatment
Aluminium
Aluminium
Copper
Ul5C Stainless Steel
U 15C Stainless Steel
U15C Stainless Steel
15 h at 250C
20 h at 100C
20 h at 100C
45 h at 360C
25 h at 300C
3 h vacuum furnace
1000C + 25 h in si
30 h at 250C
K torr 1. SK cmm2 x 10
4
110
260
450
1.6
17
14
14
11
11
11
300
17
40
:gas at
at 360C
Ref
Table 6. Polymers
Material
Kl torr 1. s-r
Araldite (moulded)
Araldite D
Araldite D
Araldite F
Celluloid
Gaflon (PTFE) (fresh)
Kel-F
Methyl methacrylate
Mylar (24 h at 95 % RH)
Nylon
Pertinax
Plexiglas
Plexiglas
Polyamid
Polyester-glass laminate
Polyethylene
Polystyrene
Polystyrol
Polyvinylcarbazol
PTFE
PVC (24 h at 95 % RH)
Teflon
Terephenil (fresh)
116
800
190
150
860
16.6
4
420
230
1200
620
12
310
460
250
23
2000
56
160
30
85
6.5
62.2
cmm2 x 10
El
0.8
0.8
0.3
0.5
0.5
0.8
0.57
0.9
0.75
0.5
0.18
0.44
0.4
0.5
0.84
0.5
1.6
0.6
0.5
0.45
1.0
0.5
0.5
35.2
220
125
73
430
3.31
1.7
140
40
600
290
27
180
230
80
11.5
200
12
80
15
2
2.5
16.8
cm-
x 10
a10
0.8
0.78
0.5
0.5
0.5
0.9
0.53
0.57
0.5
0.5
0.44
0.4
0.5
0.81
0.5
1.6
0.61
0.5
0.56
0.2
0.5
Ref
9
31
4
4
32
9
33
31
34
35
36
36
4
32
33
32
33
36
32
13
34
36
9
Table 7. Rubbers
Material
Kl torr I. s-t
Butyl DR41
Convaseal
Natural crepe
Natural gum
Neoprene
Neoprene
Nygon
Perbuman
Poliosocyanate
Polyurethane
Silicone
Viton A (fresh)
150
100
730
120
3000
300
1300
350
2800
50
1800
114
cme2 x 10
El
0.68
0.5
0.7
0.5
0.4
. 0.5
0.5
0.3
0.45
0.5
1.0
0.8
K4 torr 1. s-r
crnv2
lo8
40
49
310
60
1800
145
650
220
1270
25
440
-
cz4
Ref
0.64
0.6
0.65
0.5
0.4
0.5
0.6
0.5
0.57
0.5
1.2
-
31
33
31
33
31
33
31
31
31
32
32
9
Ref
1
1
1.7
0.7
4
32
9
9
360
Material
Kl torr 1. s-l
Steatite
Pyrophyllite
Pyrex (fresh)
Pyrex (1 month in air)
900
2000
73.5
11.6
cme2 x 10
q
1
1
1.1
0.9
95
200
5.5
1.6
cm-2
x 10
R J Elsey: Outgassing
of vacuum materials-11
Acknowledgement
AUTHORS
NOTE.
The material for these articles was originally assembled for an MSc critical survey at Sir John
Cass School of Science and Technology with helpful suggestions from Dr J L Whiteman. I am
indebted to many authors and also to The Chemical Society, The Institute of Physics, The
Macmillan Co. Inc., The McGraw Hill Book Co., Pergamon Press, and SociCtC Franqaise Du
Vide, for their permission to reproduce diagrams and tables from their publications.
361