Rolling Oil Distillation and Thermocracking Reactions in HNX and 100% H2 Annealing

E U R O P E A N
COMMISSION
SCIENCE
RESEARCH
DEVELOPMENT
technical steel research
Mechanical working (rolling)
Rolling oil distillation

and thermocracking
reactions in HNX and
100% H2 annealing
Report
hi
EUR 18634 EN STEEL RESEARCH
EUROPEAN COMMISSION
Edith CRESSON, Member of the Commission
responsible for research, innovation, education, training and youth
DG XII/C.2 RTD actions: Industrial and materials technologies
Materials and steel
Contact: Mr H. J.-L. Martin

Address: European Commission, rue de la Loi 200 (MO 75 1/10),
B-1049 Brussels Tel. (32-2) 29-53453; fax (32-2) 29-65987
European Commission
technical steel research

Mechanical working (rolling)
Rolling oil distillation and thermocracking

reactions in HNX and 100% H2 annealing
M. Lamberigts, L. Bordignon
CRM
Rue Ernest Solvay 11
B-4000 Lige
P. S. Legood
British Steei pic
9 Albert Embankment
London SE1 7SN
United Kingdom
Contract No 7210-EC/805/207
1 July 1993 to 30 June 1996
Final report
Directorate-General
Science, Research and Development
1999 EUR 18634 EN
LEGAL NOTICE
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is responsible for the use which might be made of the following information.
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It can be accessed through the Europa server (http://europa.eu.int).
Cataloguing data can be found at the end of this publication.
Luxembourg: Office for Official Publications of the European Communities, 1999
ISBN 92-828-5045-5
European Communities, 1999
Reproduction is authorised provided the source is acknowledged.
Printed in Luxembourg
PRINTED ON WHITE CHLORINE-FREE PAPER

TABLE OF CONTENTS
Page
1. INTRODUCTION ^
2. AIMS 13
3. EXPERIMENTAL 14
a. CRM Contribution 14
b. British Steel Contribution 15
RESULTS AND DISCUSSION 19

a. CRM Contribution ig
1. Oil Distillation Mechanism -jg
2. Surface Cleanliness Improvement 26
a. Compressive Stress Control 27
b. Vessel Evacuation 27
c. Oxygen Injection 28
d. Ultra-violet Irradiation 34
LABOFA TORY STUDIES
1. Degradation of Synthetic Esters and Rolling Oils 33

a. The Mechanism of Oxidative Ageing 33
b. Hydrolytic Ageing 3g
2. General Observations on Ageing of Oils and Esters 40
a. Change in Polarity Measured by SPE 49
b. GPC Analysis 4I
c. FT-IR Analysis 42
3. Degradation of Fatty Acids 43
4. Analysis of Iron Decanoate 44
5. Stepwise Ageing of Rolling Oils 45
6. Leco Analysis of a Variety of Oil Types 47
7. Analysis of Condensates from Laboratory Annealing Experiments 43
8. Laboratory Annealing and Detailed Analysis of Steel Condensates 4g
9. Investigation of Degradation with Excessive Oil Levels 50
10. Discussion of Laboratory Studies 52
a. Mechanisms of Oils Ageing 52
b. Influence of Oil Coverage on Thermal Distillation 53
c. Identification of Oil Esters other than Rolling Oils 53
PLANT STUDIES
11. FAB-SIMS Analysis of Hard Iron 53

12. Tandem Mill Monitoring over a 30-day Period 54
a. Routine Chemical Analysis Data 55
b. Particle Size Distribution Analysis 56
c. GC-MS Analysis of Extracted Emulsion 56
d. Leco Surface Carbon Analysis 57
e. Surface Chemistry Studies of Hard Iron 57
f. XPS and FAB-SIMS Analysis of Emulsions 58
13. Conclusions of Plant Trial Data 60
c. Discussion of British Steel Results 60
1. Development of Suitable Methods 60
2. Degradation Mechanisms for Oils and Esters 62
a. Mechanism of Degradation of Oils and Esters in Solution 62
b. Mechanism of Degradation of Oils and Residues on the
Steel Surface 63
3. Development of Oil Performance Indicators 64
5. CONCLUSIONS 65
a. CRM Contribution 65
6. REFERENCES 68
APPENDIX I 69
LIST OF FIGURES
Figure 1 : Batch-annealing simulator with stress application device
Figure 2: Batch-annealing simulator with stress control and oil condensation system
Figure 3: a) GC-MS trace of rotary evaporated oil extract from emulsion
b) GC-MS trace of SPE extract from previously extracted oil
Figure 4: GPC trace showing polymerisation of glyceride with ageing
Figure 5: LECO burn-off profile variation with atmosphere
Figure 6: Optimised LECO temperature ramp using nitrogen atmosphere
Figure 7: Particle size distribution of emulsion
Figure 8: Influence of compressive stresses on CH 4 evolution during annealing under 5% or
100% H 2
Figure 9: Influence of compressive stresses on surface cleanliness
Figure 10: Effect of stress level on gas evolutions during simulation batch-annealing (400C)
Figure 11 : Gas chromatography analysis of cold rolling oil at distinct stages of the process
(stress-free condition)
Figure 12: Chromatographs of reference oil and condensates recovered during various
annealing simulation cycles
Figure 13: Effect of compressive stress on condensate composition (gas chromatography
analysis)
Figure 14: Effect of compressive stress on the abundances of various carbonaceous species
left on the surface
Figure 15: Gas evolutions during stress-free batch annealing simulation No. 110 carried out to
700C under N 2 -5%H 2
700C under N 2 -5%H 2 , 0 2 being injected between 400C and 500C
Figure 17: Gas evolutions during stress-free batch annealing simulation No. 109 carried out
under N 2 -21 % 0 2 to 450C and under N 2 -5%H 2 from 450C to 700C
700C (4-hour soaking) under N 2 -5%H 2 , 0 2 being injected between 400C and
500C
Figure 19: Effects of modified batch annealing procedures on surface selective oxidation
profiles
Figure 20: Gas chromatography traces obtained on oil condensates collected after stress-free
batch annealing simulations carried out to 450C under a) N 2 -5%H 2 , b) N 2 -5%H 2
up to 350C and N 2 -21 % 0 2 over 350C, and c) N 2 -21 % 0 2
Figure 21 : Effects of distinct treatments on full hard strip surface carbon residue, as estimated
by XPS
Figure 22: Effect of 6-hour UV irradiation on cold rolled steel surface chemistry (Material
R3994; XPS spectrum section)
Figure 23: Surface elemental distributions of a UV irradiated cold rolled material (SAM
analysis)
Figure 24: Bulk elemental distributions of a UV irradiated cold rolled material (SAM analysis)
Figure 25: Oxygen uptake during oxidative ageing
Figure 26: SPE data showing change in polarity as a result of ageing
Figure 27: Oxygen uptake for saturated fatty acid ageing measured by XPS
Figure 28: Influence of atmosphere and oil coverage on carbon levels during Leco burn-off
studies measured by XPS
Figure 29: Leco burn-off profile for a gear oil
Figure 30: Leco burn-off comparison for t w o rolling oils
Figure 31 : C 1 s traces for TDMS experiments varying oil coverage
Figure 32: Degradation pathways for esters and oils
Figure 33: Variation of SAP value, stearic acid and oil % during trial
Figure 34: Mean particle size of emulsion during monitoring
Figure 35: Leco burn-off profiles for hard iron during plant monitoring
Figure 36: FAB-SIMS spectrum from hard iron sample taken during trial
Figure 37: XPS data from hard iron, emulsions and extracted oils
LIST OF TABLES
Table 1 : Residual carbon pollution after heating to 400C (mg/m2)
Table 2: Efficiency of coil intertum compressive stress relief (T m a x = 400C, N 2 -5%H 2 )
Table 3: Residual carbon surface pollution after annealing at 400C under N 2 -5%H 2 (15
MPa)
Table 4 : Effect of oxygen injections on residual surface carbon
Table 5: Effect of a UV pretreatment on strip surface cleanliness
Table 6: Coloration of oil samples on Q panels after Leco treatment
Table 7: C 1 s data for laboratory annealed samples
Table 8: FAB-SIMS analysis of high M/Z peaks of hard iron samples
Table 9: a) Stand details of tandem mill monitored

b) Emulsion tank details of tandem mill monitored
Table 10: a) C-|S data for as-received hard iron from trial
b) C 1 s data for thermally treated herd iron from trial
Table A.1.1 : Optimised parameters for Leco RC412
Table A.1.2: XPS analysis data for method development
Table A.1.3: a) FAB-SIMS interpretation of ions indicative of stearic acid

b) FAB-SIMS interpretation of ions indicative of TMP species
Table A.1.4: Interpretation of mass spectra for NPG di-oleate

SUMMARY
Steel surface cleanliness has been an important consideration for autobody grades for a number of
years. There is now, however, growing pressure to produce routinely clean material for all grades
via the batch anneal route, in order to compete with continuously annealed material.
In this framework, CRM's first objective was to investigate the influence of the compressive radial
stresses building up between the inner turns of steel coils on oil degradation mechanisms during
batch annealing. For this purpose, a laboratory simulator was developed to carry out annealing
cycles on disk-like specimen stacks subjected to controlled axial stresses. Although the latter led
to increase the measured reaction gas evolutions during simulation annealing cycles, the peak
temperature of which had been purposely kept below 400C, they were shown to increase the
total amount of carbon residue left on the surface. This suggests that rolling oil degradation is
reinforced by compressive stresses, thus leading to higher levels of thermocracking and
polymerisation. The use of pure hydrogen protective atmospheres improves final surface
cleanliness, presumably because of associated higher rolling oil hydrognation and better gas
fluxing.
In a second step, technical procedures were investigated to further eliminate oil residues from coil
turn interspaces, by acting on the thermocracking and gas-metal reactions.
Research efforts were concentrated on evaluating the effects of stress relief procedures based on
modified heat cycles. They proved successful enough in terms of surface cleanliness, but the
isothermal holdings involved would strongly reduce productivity.
Another solution, consisting in evacuating the vessel, and carrying out the heating step under a
rough vacuum to promote oil distillation, was shown to provide only marginal improvement of the
final surface cleanliness. Although exploiting distinct reaction mechanisms, alternative procedures,
aimed at helping burn out undistilled oil residues by oxygen injections, were seen to be efficient
enough. They could however not be applied industrially without proper optimisation, nor before
some practical problems have been solved satisfactorily.
Finally, ultra-violet irradiation was used on cold rolled sheet steel specimens, in an attempt to break
chemical bonds in the surface oil residue molecules and induce their oxidation or peroxidation. If
cold rolled strip UV pretreatment improves surface cleanliness, the benefit of that treatment after
annealing under N 2 -5%H 2 looks far from satisfactory.
Parallel to this, British Steel pic carried out degradation studies which showed that modification
of chain length is by an oxidative mechanism, with hydrolytic reactions occurring around the base
alcohol. In the case of oxidative ageing, reactions, forming degradation products centre on double
bonds in the ester chain. Full formulation oil packages proved resistant to change, the anti-oxidants
working effectively.
For oils on a steel substrate. X-ray Photoelectron Spectroscopy (XPS) analysis showed that under
normal coverage, thermal distillation was the predominant mechanism for oil removal, although at
higher coverage thermal degradation became important. For steel samples that do not allow easy
egress for the distillates, such as being stressed or having high oil coverage, thermal cracking
occurs, leading to species such as alkenes, aldehydes, lactones and ketones. Collection of the
distillate allows use of Solid Phase Extraction (SPE) in combination with Gas Chromatography -
Mass Spectrometry (GC-MS) to positively identify these materials.
In-situ methods of analysis were developed and applied. XPS was shown to give information
concerning the nature of the carbonaceous material, characterising a number of organics. This
technique was used throughout the project, giving information concerning the degree of
degradation, helping to build up an improved understanding of the mechanisms involved. It was
found that by thermally ageing samples at 200C on a hotplate for 30 minutes, differences could
be accentuated. Positive identification of many species was possible using FAB-SIMS, with the
exact composition of free fatty acids being of vital importance for the ageing studies.
Work using a Leco RC412 instrument on material from two different plants has shown that surface
oil cocentration alone does not define post anneal surface cleanliness performance, but the nature
of the oil and the temperatures at which it distils from the surface are also major factors. It was
shown that surface carbon measurements can be used to predict which oils may lead to problems
in annealing, whether due to intentional use, or as a result of leaks (tramp oils) in plant systems.
Further development is necessary to determine the levels of contamination which can be detected
before this can be implemented as a useful measurement.
A series of experiments were carried out to monitor the changes in an emulsion during use, in order
to link certain chemistries to surface cleanliness. The stability of the system under study resulted
in insufficient variability to be detected using current techniques. This is almost certainly as a result
of the SPC practices employed, continual small additions and alterations to the emulsions
maintaining the required performance criteria.
10
ROLLING OIL DISTILLATION AND THERMOCRACKING REACTIONS IN HNX
AND 100 % ANNEALING
1. INTRODUCTION
In order to ensure easy stamping, assembling and painting operations in finishing lines, steelmakers
must produce annealed and skin-passed deep-drawing quality sheet steel of excellent surface
cleanliness and mechanical property consistency. This is especially true for the automotive industry,
where the smooth running of drawing presses and welding robots is essential.
Two processes in the cold mill determine the final surface cleanliness: cold rolling and annealing.
For cold rolling, both the nature and quantity of rolling oil residue affect the extent of carbon smut
formation during annealing. During annealing, the annealing cycle conditions (temperature, time and
gas composition) modify the form and quantity of the residues.
In this connection, the upgrading of continuous annealing lines has certainly helped meet
customers' requirements, particularly by the introduction of a pre-cleaning step prior to continuous
annealing and through better treatment temperature homogeneity control.
Despite its utilisation flexibility and demand-adaptable investment cost advantages, classical HNX
batch-annealing does not look equally suited to meet those quality standards, because of
temperature heterogenieties inside thus treated coils. The recent development of the so-called "high
convection-high flow" technology, which involves the use of a pure hydrogen (high convection)
protective atmosphere submitted to efficient rotor-driven circulation (high flow), has changed the
picture completely and made batch-annealing a very effective competitor again.
Several research works have been - or are still being - carried out to better understand the various
gas-metal reactions taking place during such improved batch-annealing cycles, with an aim at
accounting for the resulting surface cleanliness performance and further optimising the process. In
this connection, thermodynamic models have been put forward, based on gas analyses made on
sequential pick-ups from various locations inside industrial annealing furnace loads.
In this connection, it has appeared recently that the important treatment time shortening and
associated productive capacity improvement, which the new technology leads to, may sometimes
come at a price, particularly for the common commercial quality grades, the annealing cycle of
which is the shortest.
11
As a matter of fact, the use under extreme conditions of "high convection-high flow" bell-type
furnaces of at least one of the designs now available leads to deliver more heat inside the coil eye
during heating. This results in the occurrence of steep transient local temperature gradients and
associated inter-turn compressive radial stress build-ups between 300C and 400C, when the
most effective de-polluting rolling oil residue decarboxylation and thermo-cracking reactions should
normally take place.
Consequently, subsequent carbon-removing gas-metal reactions (Boudouard and Fischer-Tropsch)

do not proceed as expected, because the metal surface has not been as thoroughly de-oxidised.
The net result is worse final cleanliness (carbon residue and imperfectly back-sintered iron fines)
in the first inner turns than in the rest of the coil, with higher undesired selective oxidation.
It can therefore be concluded that gaps remain in our understanding of the mechanism of
degradation during the use of rolling oils and of thermocracking reactions which occur during
annealing. Lastly, the application of this work has not yet been achieved on a routine basis.
As far as residual strip surface pollution is concerned, work carried out at CRM, HOESCH, IRSID,
British Steel and elsewhere has examined various aspects of the problem previously )(2)(3)(4)(5)
For example, CRM have developed analytical techniques to characterise the major components of
rolling oils (both natural and synthetic). This work has been expanded on by IRSID, who have also
explored novel ways of extracting and analysing surface organic residues'61. Work at HOESCH has
explored the hydrolytic ageing of oils, especially a study of the importance of metal soap formation.
Previous work at Welsh Technology Centre has included an examination of the annealing burn-off
characteristics of a number of synthetic ester types, esters with different fatty acid make-up, the
role of anti-oxidants and the modelling of mill performance (with respect to surface cleanliness)
using laboratory ageing techniques' 71 . Purely oxidative ageing degradation mechanisms have also
been studied. Thus a number of the analytical techniques required to examine the rolling oil
components and surface organic residues have already been developed.
In the main, these techniques have involved extraction of the oils and residues from the strip
surface, followed by the analysis of the extract. This approach has provided invaluable information
concerning degradation of the oils in service, but fails to address two particular points. Firstly, does
the extracted oil represent that originally on the surface - modification of the oil during extraction
and analysis is a distinct possibility. Secondly, little work has been carried out on the extraction
efficiency of the residues. Some doubt, therefore, exists as to whether this ex-situ approach
provides a full description of the rolling oil chemistry.
12
Although work on the base esters has provided much information on the relative performance of
the different structures and fatty acid make-up in terms of steel surface cleanliness, certain
anomalies remain in interpreting the results of laboratory experiments and in correlating them with
full scale trials.
It also appears highly desirable to predict the behaviour of new rolling oils. This would reduce the
need for potentially costly full scale trials, and would consist of a suite of analytical methods and
experiments. To accomplish this goal, current oils must be monitored throughout use, to identify
those elements that have a bearing on the surface cleanliness. Correlations with mill data will then
allow the proposed tests to be identified and carried out on laboratory samples.
2. AIMS
The importance of steel surface cleanliness for autobody and drumstock grades has been clear for
a number of years. It was the intention of this project to understand the mechanisms affecting final
surface cleanliness and develop means by which it can be better understood and controlled.
The research was organised in complementary pieces of work, jointly carried out by CRM and
British Steel pic, with an aim at:
a) Further understanding the degradation of oils and esters;

b) Assessing the effect of compressive radial stresses building up between the inner turns of
steel coils during the initial heating stage (below 400C) of batch-annealing treatments
carried out under HNX (5% H2) and 100% H 2 on the distillation and thermocracking of
rolling oil residues;
c) Developing in-situ analysis techniques to provide for a better understanding of the carbon-
based species left on the surface;
d) Using this new knowledge to benefit the cold mill.
Based on the thus obtained better understanding of gas-metal reactions, solutions will eventually
be put forward to help better select rolling oils and further eliminate oil residues from inter-turn
spaces, by modifying the thermocracking reactions taking place during batch-annealing.
13
EXPERIMENTAL
3.a. CRM Contribution
Better surface cleanliness and homogeneous mechanical properties can be achieved by using 100%
H 2 batch-annealing protective atmospheres. In parallel, increasing the under-cover gas flow allows
to shorten the heat cycle, which leads to productivity improvements.
Combining those t w o technologies on an industrial scale has however brought back a residual
pollution problem for the inner turns, close to the coil centre chimney (eye)'81. This carbon pollution
is associated with intense compressive stresses which build up on heating.
The development of a laboratory simulator (figure 1) has made it possible to monitor the gas evolu-
tions taking place in the course of a heat cycle, very similar to that of an actual batch-annealing
treatment. The cycle is imposed to a stack of specimens subjected to a freely adjusted compressive
stress level. The system also incorporates an organic vapour condenser at the outlet of the furnace.
Condensates, collected after various

( BATCH ANNEALING SIMULATOR )
cycles carried out under distinct stress THREADED
RODS
and atmosphere conditions can be analy-
sed by gas chromatography. Volatile
THERMAL
fractions which cannot be condensed at INSULATOR
room temperature are analysed conti- FURNACE 25 SAMPLES

BELOW f 50 mm
nuously by mass spectrometry (CH 4 ,
STAINLESS
C 2 H 4 , C 0 2 , H2) or by other specific STEEL THERMOCOUPLE
GAS INLET
methods (CO, H 2 0). Finally, surface 0.2 l/h
cleanliness is assessed by organic re- 50 mm

0101051
sidue combustion under oxygen flow.
il il ^H~ <= rm
Figure 1 : Batch-annealing simulator with stress

application device
The simulator described above soon proved not to be flexible enough for all the test parameters to
be tested (compressive stress relief at various stages in the heating step, etc) This required the
construction of a new simulation furnace (figure 2).
14
The latter can treat stacks of up to 50 iza
disk-like specimens, 50 mm in diameter; Dew
Point
it has made it possible to:
Mass
a) Carry out simulation heat cycles Spectrometer
under variable levels of compressive Oil
Collector
stress,
b) Assess the gas evolutions taking
place during the annealing cycle in Vacuum
Pump
' Thermocouples
a quantitative way,
c) Collect oil vapour at the outlet and
analyse condensed species by gas
chromatography, and Figure 2 : Batch annealing simulator with stress control
d) Evaluate the corresponding effect and oil condensation system
on surface cleanliness, based on

residual carbon measurements.
Parallel to this, annealing laboratory simulation cycles were carried out on cold rolled specimens
having undergone an initial UV radiation treatment, to improve oil residue distillation properties.
Other techniques were also tested, among which vessel evacuation, oxygen injection certainly
deserve special mention.
3.b. British Steel Contribution
The British Steel contribution involved the development of several analytical techniques, the
detailed descriptions of which are given in appendix I.
Use of SPE (Solid Phase Extraction) in subsequent analysis by techniques such as GC-MS gives a
fast and selective extraction of polar materials from an oil sample (figure 3). These polar species
are likely to be the materials of interest in surface cleanliness studies, having a greater potential for
chemical adsorption to the steel surface. A single extraction can be carried out in under 5 minutes,
at low cost and minimal solvent usage. Another chromatographic technique, GPC (Gel Permeation
Chromatography) was developed and the method used tested for ruggedness (figure 4).
15
Abundance
1600000
1400000
1200000
1000000
800000
600000
400000
UUMII,
200000 JJ^LJL^^.
JL~j*^JL~***d^
\
Time>6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00
Figure 3. a : GC-MS trace of rotary evaporated off extract from emulsion
Abundance
5500000
5000000
4500000
4000000
3500000
3000000
2500000
2000000 ;
1500000^
1000000
500000 1
.,.*,, . . . U , Vtr^.VrriVrr^^ 1^l""l I I I T
Time->-10.00 11.00 12.00 13.00 14.00 15.00 16.00 17.00 18.00 19.00
Figure 3. b : GC-MS trace of SPE extract from previously extracted oil
16
8 Earlier retention
I time corresponds
to larger molecules
ra
I 0.6 Unaged
g 0.4
cn
Hydrolytically
I 0.2 aged
S
5 6 7 8
Retention time (minutes)
Figure 4 : GPC trace showing polymerisation of glyceride
with ageing
2000 1,200
190 232 298 369 443 514 586 653 654

Temperature (C)
Figure 5 : LECO burn-off profile variation with atmosphere
Time / nominal units
Figure 6 : Optimised LECO temperature ramp using nitrogen

atmosphere
17
Development of the Leco RC412 operating conditions has allowed potentially informative data
concerning the burn-off of surface carbon from steel sheets to be assessed. Initial problems with
reproducibility have been overcome, with a complex temperature programme and use of an inert
atmosphere to prevent oxidation of residues (figures 5 and 6). As well as gaining quantitative data,
qualitative data may be of use in identifying changes in an oil composition either as a result of
degradation in use, or as contamination of an emulsion system occurs.
In general, XPS (X Photoelectron spectroscopy) shows that there is a correlation between the C 1s
and the 0 1 s high resolution spectra observed for most samples examined. Thermally aged oils
showed an increased area due to C-0 species, indicating that XPS can be used to give an indication
of ageing. A notable change in the peaks corresponding to the Fe 2p binding energies was also
observed for the thermally treated (200C) hydrolytically aged formulation, further evidence that
the majority of metal complexes formed are iron based.
Interpretation of the C 1 s spectra reveals an increase in oxidation for the majority of samples after
heating. Data from samples at 200 C show that the full formulations have oxidised to a lesser
extent than samples free of additives. A number of samples showed evidence of metal
carboxylates. These species were found to be present in the full formulation and liquid glyceride
samples, but not in the those extracted from the emulsion. The absence of these species may be
due to the extraction procedure, carboxylates remaining in the aqueous layer. It was also interesting
to note that the NPG di-oleate samples were free of metal carboxylates, indicating that even
without additives, this is not easily hydrolysed. It can therefore be concluded that the XPS
technique has been developed sufficiently to provide details assisting in characterising an oils
performance with regards to surface cleanliness.
Use of the FAB-SIMS (Fast Atom Bombardment - Secondary Ion Mass Spectrometry) in-situ analysis
complements the information given by the high resolution spectral data from the XPS method. In
contrast to the functionality information that is provided by the XPS, FAB-SIMS can offer a positive
identification of the compounds present on a steel substrate for a relatively simple material. It is
anticipated that with experience and familiarisation with this instrument and sample type, details
may be forthcoming from the considerably more complex residues present on plant material.
TDMS (Thermal Desorption Mass Spectrometry) experiments followed a similar course to

FAB-SIMS, identifying ions present in a simple starting material. Interpretation of the mass spectra
from a limited number of thermally aged samples showed a decrease in the number of unsaturated
acids coupled to an increase in the number of iron-organics with ageing. As in the case of
FAB-SIMS, it is anticipated that greater use of this technique will ensure that it will be of use for
analysis of steel processed through the Cold Mill.
18
Particle size determination methods for emulsions have been developed in the laboratory, Malvern
instrumentation proving considerably more suitable than image analysis equipment. Accepting that
samples cannot be processed quicker than 30 minutes after sampling, there seems to be little
variation with time for Malvern determinations. Problems can occur at high pump speeds, air being
incorporated into the sample, giving rise to spurious peaks. It is unclear how small a change in
particle size distribution this method can reliably detect, this being its potential use in plant
monitoring studies (figure 7).
10 Volume % 100
90
80
\
f 70
I 1
60
( 50
40
30
\ 20
\
10
rf
0 0
0.1 1.0 10.0 00.0
Particle D i a m e t e r (.)
Figure 7 : Particle size distribution of emulsion
4. RESULTS AND DISCUSSION
4. a. 1. Oil Distillation Mechanism

In a first stage of our research, purposely restricted to low temperature reactions (de-carboxylation,
distillation, thermocracking: s 400C), CH 4 evolutions have systematically been observed to be
more intense in the case of under-stress cycles, whatever the type of atmosphere (HNX or H 2 :
figure 8). Table 1 gives the levels of surface carbon pollution measured after identical heat cycles
carried out under distinct stress levels. The results confirm both the global cleanliness advantage
provided by pure hydrogen atmospheres and the compressive stress detrimental effect. This higher
surface pollution obtained after annealing under stresses, can be observed on the surface as a black
deposit as shown on figure 9.
19
_o_ 5%H2-0MPa
_._ 5 % H 2 - 1 5 M P a
_^_ 100 % H 2 -OMPa
_^_ 100 %H2- 3MPa
- ^ 100 % H 2 -15MPa
1 2 3
TIME (HOURS)
Figure 8 : Influence of compressive stresses on CH4 evolution during annealing under

5% or 100% H2

i LABORATORY SIMULATION
THERMAL CYCLE
400-
NO STRESS

'3100-000
COMPRESSIVE STRESS:
15 MPa
Figure 9 : Influence of compressive stresses on surface cleanliness
20
CH 4 evolutions then account very poorly for the total hydrocarbonaceous emanation resulting from
residual oil distillation and thermocracking. Figure 10 compares the integrated gas evolutions
measured up to 400C, thus showing that the fractions of other species (C 2 H 4 , C 0 2 , CO) also
increase with stress level.
Stress level
Atmosphere OMPa 3MPa 15 MPa
5% H 2 6,5 10
100% H 2 4 5,5 8,5
Table 1 : Residual carbon pollution after heating to 400C (mg/m2)
These results could advantageously be completed by analysing the condensates obtained under
distinct experimental conditions.
3
-- '
Q)
? -

15 MPa
3 MPa
C2H4 NO STRESS
C02
Figure 10 : Effect of stress level on gas evolutions during simulation batch-annealing (400C)
21
ANNEALING: 4 0 0 ' C - WITHOUT STRESS
THERMOCRACKING MINERAL
nr
PRODUCTS OIL
e
oc FRESH
M. M ^
OIL
AFTER C O L D (EXTRATED
Q 4 A..JÛ-~ " ROLLING FROM SURFACE)
g -I. t i i Ij j
^
u_
( I'.UJ^*: 100 %H2 DISTILLED AT 400eC

AND CONDENSED

^>
I 5%H2 FRACTION
0100030P
RETENTION TIME
Figure 11 : Gas chromatography analysis of cold rolling oil at distinct stages of the process
(stress-free condition)
In this respect, figure 11 shows how much the rolling oil chemistry can be modified from early-
stage pickled strip oiling (fresh oil), to intermediary cold-rolling and final annealing.
These results were obtained by gas chromatography, whereby the various organic fractions, which
are characterised by distinct molecular chain lengths, can be separated in the distillation column.
As a matter of fact, they emerge from it after distinct retention times for a given temperature ramp.
It is thus possible to distinguish between:

a) esters, making up the oil lubricating fraction,
b) mineral oils, giving rise to a broad peak, characteristic of a group of alkane molecules of va
rious weights, and
c) degradation products, created by the transformation.
The analysis of surface residues extracted from the strip shows that degradation products are
already present right after cold-rolling, because esters are modified under the combined effects of
rolling stresses and oil heating in the rolling gap. In order to assess batch-annealing surface de-
pollution efficiency, it would then be interesting to analyse the oil fractions distilled during the
treatment carried out under HNX and pure H 2 , after they have been condensed in a cold trap at the
outlet.
22
Figure 11 also confirms that organic esters are eliminated in both annealing cycles. The mineral
component is always detected, but shows differences between HNX and H 2 , in terms of both major
peak position and secondary peak intensities. Degradation products are systematically observed,
particularly for annealing under pure hydrogen.
This could well be accounted for by the more intense ester hydrogenisation after cold-rolling, thus
inducing their cracking into shorter molecular chains, easily removed from between the specimens
stacked in the furnace. The same observation also explains, at least partially, the better cleaning
efficiency of batch-annealings carried out under pure hydrogen.
In an attempt to better assess rolling oil distillation temperatures, several stress-free annealing treat-
ments were performed under N 2 -5% H 2 , up to various maximum temperatures (ranging from 250C
to 400C). Figure 12 shows the retention time evolutions of chromatographic signal intensities
pertaining to condensates collected at the outlet of the furnace. The fresh oil chromatogram is also
shown, for comparability reasons.
THERMOCRACKING MINERAL ESTERS

PRODUCTS OIL
ANNEALING
TEMPERATURE
(5%H2)
FRESH
OIL
0100037 RETENTION TIME
Figure 12 : Chromatographs of reference oil and of condensates recovered during various

annealing simulation cycles
23
As before, each line can be divided in three distinct segments:
a) a pattern of sharp low molecular weight peaks (short retention times), pertaining to the rolling
oil thermocracking fraction. Obviously enough, the fresh oil does not contain these
compounds, which already appear over 250C. Mass spectrometry measurements on outlet
gas pick-up also reveal the presence of more volatile species (CH 4 , C 2 H 4 , etc.).
b) a broad peak, associated with alkane-type molecules of various weights, corresponding to the
mineral oil fraction. It shifts to longer retention times with increasing maximum cycle tempera-
tures, thus suggesting that some threshold temperature must absolutely be overcome to
ensure the complete distillation of heavier mineral oil fractions. On the other hand, the compari-
son with the reference chromatogram reveals the rapid elimination of uncondensed lighter
fractions. The latter must still remain uncondensed at the outlet and take part in the formation
of the volatile species detected by mass spectrometry.
c) an additional series of sharp peaks, associated with synthetic esters. The latter are fairly
abundant in the fresh oil, but survive in only a limited amount in the condensates. Conse-
quently, they can be considered responsible for a great deal of the thermocracking products
detected by chromatography at short retention times.
Even at a low level, compressive stresses (3 MPa) modify the chromatograms in a very substantial
way, by decreasing their three components described above (figure 13). Some compounds (light
thermocracking fraction, synthetic esters) can even disappear completely, while an increase in the
amount of more volatile species is observed by mass spectrometry.
These observations can be accounted for by the strong diffusivity reduction of long organic chains
trapped between specimens pressed against one another. Their longer residence time increase their
thermocracking, thus leading to the reinforced evolution of volatile species (CH 4 , C 2 H 4 ), and to the
adhesion at the surface of a greater deal of degradation products.
24
ANNEALING: 400 eC - 5 % H2
THERMOCRACKING L
^ ESTERS
PRODUCTS
~A
A t
oc
O
t
O
LU I I ! I, , , ifW* *A
tu
Q
N O STRESS

'*,
>_........
1-
LU
W I T H STRESS (3 M P a )
>*M
0100037 RETENTION TIME
Figure 13 : Effect of compressive stress on condensate composition

(gas chromatography analysis)
This is clearly s h o w n by figure 1 4 , based on XPS ANALYSIS AFTER BATCH ANNEALING

SIMULATION AT400C
XPS analysis results pertaining t o specimens
0100025
having undergone simulation batchannealing
between 2 5 0 C and 4 0 0 C w i t h and w i t h o u t
compressive stresses. As a matter of fact, XPS
carbon peak C 1 s can be decomposed into
several components accounting for various
chemical bonds, thus providing a clue concer
ning t h e nature of the organic molecules
present at t h e surface. This w a y , t h e abun
dance of "tarlike" componentassociated CC
bonds is seen t o increase regularly w i t h cycle
peak temperature, while t h a t of C bonds,
representing little or nondegraded oil, decrea
ses. CC bonds also increase w i t h the stress Figure 14 : Effect of compressive strass m ft
level, t h u s confirming the results of f i g . 13. abundances of various carbonaceous spmeks
left on the surface
25
This set of results suggest that batch-annealing heating-stage compressive stresses strongly
increase rolling oil thermocracking, by hampering the diffusion and free distillation of long molecular
chains trapped in the inter-turn species. This is particularly true under high gas flow conditions.
These molecules remaining longer at the surface degrade further, which increases the evolution of
volatile gasses (CH 4 , C2H4) and the adherence of tar-like compounds obviously detrimental to final
product cleanliness. The use of 100% H 2 protective atmospheres alleviates the problem, by
favouring the formation of shorter chains (hydrogenisation effect), and by increasing the fluxing of
inter-turn spaces.
4. a. 2. Surface Cleanliness Improvement

It has been made very clear that most rolling oil residues must be eliminated at an early stage in
the annealing cycle (below 400C), so that the formation of a tar-like deposit induced by
thermocracking reactions can be minimised. The latter is indeed very difficult to remove through
higher temperature reactions (Boudouard, Fischer-Tropsch, direct methanation, etc.).
Previous CRM research works' 9 ' have indeed shown that in industrial batch annealing furnaces, a
high temperature water injection (600C) can improve final surface cleanliness, but is very difficult
to keep under perfect control. Therefore, our efforts have been concentrated on the low
temperature part of the treatment. Four distinct orientations were selected:
a) Improvement of oil distillation by relieving the inter-turn stresses
b) Improvement of oil distillation by evacuating the furnace at some stage of the cycle heating
step (laboratory simulation furnace),
d) Oil residue burnout and iron oxide formation during the heating step carried out in air. After
the subsequent evacuation of the furnace and re-establishment of the hydrogen-containing
atmosphere, iron oxide should have been reduced by hydrogen at higher temperature, thus
producing water vapour capable of reacting with the tar-like residue,
e) Cold-rolled strip surface oil U.V. irradiation prior to batch-annealing, in order to transform into
shorter, more easily distillable organic compounds.
Ultimate cleanliness after complete annealing (700C) had to be verified in each case. This required
the construction of a new simulation furnace (figure 2).
The latter can treat stacks of up to 50 disk-like specimens, 50 mm in diameter; it has made it
possible to:
a) Carry out simulation heat cycles under variable levels of compressive stress,
b) Assess the gas evolutions taking place during the annealing cycle in a quantitative way,
c) Collect oil vapour at the outlet and analyse condensed species by gas chromatography, and
26
d) Evaluate the corresponding effect on surface cleanliness, based on residual carbon
measurements.
Parallel to this, annealing laboratory simulation cycles were carried out on cold rolled specimens
having undergone an initial UV radiation treatment, to improve oil residue distillation properties.
a. COMPRESSIVE STRESS CONTROL
In a first series of low temperature tests (T max = 400C) carried out under N 2 -5%H 2 on stacked
R4885 cold rolled steel specimens, the preset compressive stress (15 MPA) was artificially relieved
at various temperatures, between RT and 400C. Bearing in mind that the material's initial surface
carbon pollution was 127 mg/m 2 , table 2 shows that the procedure is very efficient, provided the
compressive stress is removed at a sufficiently low relief temperature T re |.
""rel <C)
25 250 300 350 400
mg/m2 C 20 15 12 12 37
Table 2 : Efficiency of coil interturn compressive stress relief (Tmax=400C, N2-5%H2)
Unfortunately enough, stress relief can only be achieved in practice by introducing sufficiently long
isothermal holdings, which strongly reduces productivity (slow heating). The method must therefore
be considered as industrially non-viable.
b. VESSEL EVACUATION
As was already mentioned above, another possibility consists in evacuating the vessel ( 1 0 1 Torr)
at the beginning of the annealing cycle, in order to facilitate the extraction of organic compounds
from the coil turn interspaces. Under the experimental conditions considered for our laboratory tests
entirely carried out under 15 MPA on stacked R5223 cold rolled steel specimens, this procedure
however provides only marginal improvement of the final surface cleanliness (table 3).
27
Evacuation temperature range (C)
No evacuation 200-250 250-300 300-350
mg/m 2 C 163 14.52 143 121
Table 3 : Residual carbon surface pollution after annealing at 400 C under N2-5%H2 (15 MPa)
Moreover, it brings about practical application difficult problems, in relation with the mechanical
response of the hood and the tightness of the system.
c. OXYGEN INJECTION
Whatever the injection temperature (between 25 and 450C), oxygen can be added to the
annealing atmosphere to burn out oil residues, while inducing some degree of iron direct oxidation.
Thus created surface oxide can be reduced by hydrogen at higher temperature, which forms the
water vapour that is needed to react with hydrocarbon residues to improve final surface cleanliness.
Table 4 summarises the results of 16 simulation cycles to three distinct peak temperatures T m a x ,
which were applied to specimens taken from cold rolled steels R5223 and R5343, respectively
characterised by initial surface carbons of 47 and 176 mg/m 2 .
T m a x <C)
Steel Atmosphere 450C 700C 700C-4h
R5223 N 2 -5%H 2 5,5 1-1,5

(47 mg/m2) 0 2 (350 to 450C) 4 3
21 % 0 2 3,5 1
R5343 N 2 -5%H 2 9,8 6,8 5,3

(176 0 2 (350 to 450C) 5 5,4 5,5
mg/m2) 21 % 0 2 5,2 4,1
Table 4 : Effect of oxygen injections on residual surface carbon
Figures 15 to 18 illustrate thus obtained gas analysis results. When oxygen is introduced in the
atmosphere from the outset (from room temperature), substantial amounts of CO and C 0 2 are
detected in addition to the classical evolution of C n H m , which reflects oil combustion. The latter
however remains incomplete (presence of C n H m ), either because oxygen has not been injected to
a sufficient amount, or because it diffuses only sluggishly between the coil turns.
28
(5% H 2 -O MPa)
5%H 2 -0MPa
0 2 400-500C (TQR 5223)
o e.
UJ
cr
<
LU
Q.
-1 1 1
5 10 15 20 - TT
TIME (HOURS) 5 10 15 20
TIME (HOURS)
5 10 15
0 r^H4 5 10 15 TIME (HOURS)
* TIME (HOURS)
Figure 15 : Gas evolutions during stress-free Figure 16 : Gas evolutions during stress-free
batch annealing simulation No. 110 carried batch annealing simulation No. 119 carried
out to 700C under N2-5%H2 out to 700C under N2-5%H2, 02 being
injected between 400C and 500C
29
,
' O % H 2 450C
5% H 2 0 MPa
5%H2700"C
O MPa 21%O 2 400500C,
800
700
600
O
500 tur
oc
400
i
ce

s.
LU
r
5 10 15
TIME (HOURS) 5 10 15
TIME (HOURS)
TIME (HOURS)
TIME (HOURS)
Figure 17 : Gas evolutions during stress-free Figure 18 : Gas evolutions during stress-free
batch annealing simulation No. 109 carried batch annealing simulation No. 136 carried
out under N2-21%02 to 450C and under out to 700C (4-hour soaking) under
N2-5%H2 from 450C to 700C N2-5%H2, 02 being injected between
400C and 500C
30
When introduced at higher temperatures (350450C), oxygen can react with oil residues and with
iron, in accordance with the equations below:
Cîdue ' f A COÔ

t (H
Fe | 0 2 FeOx
The establishment of a HNX (5% H2) protective atmosphere for the remainder of the treatment then
leads to the following reactions:
H 2 Vz 0 2 - H 2 0
FeO x * H 2 - Fe H 2 0
C H 2 0 - CO H 2
CO H 2 0 * C 0 2 + H 2 (2)
the last three of which are strongly reinforced when oxygen is injected in the atmosphere at a low
temperature (below 450500C), because the surface oxide layer then becomes thicker. Figure 18
shows that the H 2 0 content decreases only after a twohour holding time at 700C, which
corresponds to the complete reduction time of the iron oxide. This retarding effect has no
deleterious consequences in the case of long duration industrial cycles.
In the case of steel R5343, the protective atmosphere CO content after an annealing treatment
at 700C is systematically twice as big as it is for steel R5223 (710% vs 34%), which also
corresponds to a higher amount of surface carbon residue (table 4). This can be accounted for by
assuming that CO is not eliminated fast enough from the atmosphere, due to an insufficient gas
flow in the furnace, thus leading to gas equilibration by the gaswater reaction (4th in group 2
above), and an associated arrest of depolluting reactions.
In an effort to test the assumption, it would be interesting to perform the same heat cycle, while
substantially increasing the gas flow, once the sample temperature has reached 700C (i.e., when
the CO evolution is maximum). The duration of the oxidising sequence (oxygen injection) should
moreover be increased, to generate more water vapour and thus help improve the depollution (3rd
reaction in group 2 above).
The data reported in Table 4 show very clearly that an oxygen injection can result in a significant
improvement of the sheet surface cleanliness, when it is applied either immediately after rolling oil
distillation or for the whole cycle. As was already mentioned earlier, final surface cleanliness
strongly depends on cold rolled material cleanliness. Consequently, "dirty" cold rolled sheets could
be made cleaner by resorting to both an intense gas flow and an important degree of oxidising
during annealing.
31
The treatment can obviously not be considered a success unless the thus created iron oxide is fully
reduced by the high temperature part of the cycle, carried out under N 2 5%H 2 . Therefore, a
systematic SIMS investigation was carried on specimens having undergone batch annealing
simulations characterised by distinct air injection sequences.
For each condition considered, figure Oxygen Profiles

T1T2: air injection
temperature range
19 compares negative secondary ion
current profiles pertaining to oxygen,
aluminium oxides and manganese
FeO, at 550C
oxides (cesium primary ion beam).
\
Total oxidation
350C450'C atSSO'C
It is seen that classical HNX batch

2500 5000 7500 10000 12500 15000
annealing induces the selective oxida Sputtering time (s)
tion of both Mn and Al, which are
Cs- AIO. Profiles
major alloying elements of ELC steel
1E+5
grades. Air injection between 350C
and 450C brings about more inter
1E+4 ^sctsoc ^X
| 1E + 3
nal selective oxidation and less exter socssoc
1E+2 \\5%H2
S 350"-450"
nal oxidation, which would normally
1E+1
jrf FeOx at 550C
prove beneficial to the response to 1E+0
electrolytic zinc coating or paint pre 2500 5000 7500 10000 12500 15000
Sputtering time (s)
paration treatments. All the iron
oxide created during the air injection MnO. Profiles
Cs
is eventually reduced at higher tem
perature by N 2 5%H 2 , thus leading
the oxygen profile to be fully accoun
ted for by selective oxidation. As a
matter of fact, total oxidation, as can
for instance be obtained by reheating
2500 5000 7500 10000 12500 15000
the sample in air to 550C, always Sputtering time (s)
leads to a much stronger oxygen
signal, as can be seen in the figure Figure 19 : Effects of modified batch annealing
19. procedures on surface selective oxidation profiles
If air is injected from room temperature to 450C, the oxygen profile extends over a longer in-depth
distance from the surface than is the case for injections between 350C and 450C. This is clearly
correlated to a stronger selective oxidation of Mn and Al.
32
For air injections between 350C
Annealing conditions :
and 550C, a substantial iron
oxide layer is seen to survive bet- 5%H2-450C
ween the internal oxidation and

the reduced iron at the surface.
In total, these results suggest that

the oxidation generated by low 5%H2 between 25C and 350C
0%H2-21%O2 between 350C and 450X
temperature air injections (<.
450C) can be eliminated by the
rest of the cycle under a reducing
protective atmosphere.
In an attempt to complete the

21%02 450C
information, gas chromatography
analyses were performed on
condensed oils collected at the
furnace outlet. Typical spectra,
obtained after annealing cycles
carried out at 450C under va- Retention time (a.u.f
96106
rious atmospheres, are illustrated

by figure 20. It appears very clear- Figure 20 : Gas chromatography traces obtained
on oil condensates collected after stress-free batch
ly that, when oxygen is injected annealing simulations carried out to 450C under a)
after oil distillation (350-370C), N2-5%H2, b) N2-5%H2 up to 350C and N2-21%02
over 350C, and c) N2-21%02
the chemistry of condensed oils
remains unchanged, leading the spectra to exhibit a broad mineral fraction peak, together with
synthetic ester decomposition-associated sharper lines, corresponding to well defined retention
times. The latter sharper lines correspond to hydrocarbon molecules containing between 20 and 40
carbon atoms, which suggests they are esters having lost 1 or 2 fatty acids.
On the other hand, when oxygen is injected from the outset (figure 20.c, 2 1 % 0 2 ) , the broad
mineral fraction peak is kept the same, but ester degradation is more complete, which results in the
occurrence of lighter molecular fractions. The latter can however not be identified as free fatty
acids.
33
For the heat cycles illustrated by figure 20 (T m a x =450C), the creation of those lighter molecules
accounts at least partially for the surface cleanliness being better after annealing under oxygen. It
can however also be speculated that oxygen can react directly with those carbon residues which
would not have distilled at any rate under classical HNX annealing conditions.
As a conclusion, it can be said that oxygen injection at the beginning of the annealing cycle can
significantly improve final surface cleanliness. Further tests will be carried out in the future to
optimise the conditions of its application in terms of both injection sequence and underhood gas
flow control, in an attempt to achieve the same degree of quality as in continuous annealing (2
mg/m 2 C).
d. ULTRA-VI OLET I RRADI ATI ON
UV radiations can be used to break some chemical bonds, because their wavelengths (UVB : 280
320 nm) are shorter than those corresponding to binding energies between parts of the organic
molecules involved in this problem. The point can be illustrated by saying that a "CC" bond can
be broken by an energy input of 82.6 kcal/mol (wavelength =346.1 nm), while 289.7 nmand
334.4 nmwavelength radiations can respectively destroy "C" and "CO" bonds.
UV radiations moreover produce some ozone, thus providing a possibility of organic molecule
oxidation or peroxidation' 1 K Some thermal
effect cannot be ruled out, inasmuch as %At.C
% At. C (Ref)
temperature between 110 and 130C have 1.2
been recorded on sheet specimens, 0.7 mm
Reference
in thickness, submitted to the radiation of a
100W Hg vapour lamp positioned at 2 cm
from their surface. Obviously enough, care
must be exercised when evaluating actual 6
surface temperatures, because surface heat
conductivity is not known very accurate
,y(11).
UV: 6 hours
In an attempt to confirm the predominant 15 20

role of the photochemical effect, we have Z(eq. Fe)
tried to achieve the same temperature by IR Figure 21 : Effects of distincts treatments on

irradiation (250W lamp). Figure 21 makes it full hard strip surface carbon residue,
as estimated by XPS
34
very clear that a 2minute IR irradiation is definitely less efficient than its UV counterpart to
decrease the residual surface carbon level:
at%CIR
1 (3)
at%C,'reference
Beyond its depolluting effect, UV irradiation has also led to reveal the presence of Si in a surface
pollution film. In this connection, figure 22 gives the Si XPS spectrum window that was recorded
at the very surface ( Z = 0 nm) of a sheet specimen having undergone UV irradiation, showing that
Si is in an oxided condition.
I (c/eV. s)
700
600
Irradiated UV 6 hours ._ .y v " ~'%<m ' '^r+y::\y:r;>?
500 _
Si (2p)
Z=0A
400-
300- As Cold Rolled

."/.-v-V"'4 .\./^,>^^.//:,.-.-'.
200-
Z=0A
100-
96121
0
f
110 105 100 95
115 BE (eV)
Figure 22 : Effect of 6-hour UV irradiation on cold rolled steel surface chemistry

(Material R3994 ; XPS spectrum section)
With an aim at clarifying the origin of Si, the following experiment was carried out:
a) mask the reference cold rolled sheet specimen partially, by placing a circular Pt diaphragm
(=100) on it,
b) irradiate it under UV for 6 hours, and
c) compare the XPS spectra recorded in the irradiated and masked areas.
35
The specimen was eventually polished (removed material thickness of about 0.1 pm), submitted
to a new round of UV irradiation (diaphragm+ UV/6h), before the XPS spectra were recorded again.
The comparison of thus obtained results clearly suggests that the detected Si did not originate in
the metal matrix (figures 23 and 24).
~N
r
Sample exposed to UV light : BEFORE polishing J
Fe Z (A)
T T ; : &:'*; ~ '
0
F -T-^*?^-- '"-
SS118
Figure 23 : Surface elemental distributions of a UV irradiated cold rolled material (SAM analysis)
>
Sample exposed to UV light : AFTER polishing.
^ Fi C ' (A)
'f' -i-gPS&. 'J.. i^VS ' '. 0
SK'.r.
oc?;'''^*' i ?SS3* ^ ? . ' ^ , r ' . J . g 8 S "Csa?:^'*??
SSI'S
F/jgrure 2 4 ; Bulk elemental distributions of a UV irradiated cold rolled material (SAM analysis)
36
As a matter of fact, the central area and corona' 1 ' of the specimen that was irradiated in the
unpolished condition exhibits some degree of carbon attenuation, accompanied by a reinforcement
of Fe, O, and Si intensities. In the polished specimen, the intensity of Si is nil, while those of Fe,
O and C remain uniform across the central zone (no central disk nor corona).
It is therefore very likely that those Si residues appeared during the sheet cold processing
operations, presumably in connection with the rolling oil, which sometimes contain poiysiloxane-
based anti-foam agents.
Some other trials has been carried out to check the influence of a such treatment at various stages
of the process. Table 5 summarises the effects of such UV irradiation:
HNX up to
Full HNX 350C Full air
air 350-450C
CR* (176 mg/m2) 9,8 5 5,2
CR + 3 0 m i n UV (103 8 7,6 5,7

mg/m2)
* CR: Cold Rolled
Table 5 : Effect of a UV pretreatment on strip surface cleanliness
UV irradiation is already seen to improve surface cleanliness in the as rolled condition (from
176 to 103 mg/m 2 surface carbon). The effect results presumably from the combination of
direct irradiation and associated heating effects (110 to 130C).
After classical batch annealing under N 2 -5%H 2 , little cleanliness improvement is observed,
which suggests that the amorphous compounds left behind by UV irradiation-induced organic
molecule breakup cannot distil easily during the annealing cycle.
After annealing cycles involving air injection periods, the cleanliness of untreated specimens
even seems worse than that of their untreated counterparts, thus indicating that post-
irradiation residues do not react so readily with oxygen as current rolling oil organic
compounds.
1
The corona effect results from UV light diffusion and multireflection phenomena taking
place at the edge of the diaphragm, which tends to reinforce the light flux in that area.
37
Following the development of suitable methods, laboratory studies were made on esters and oils
to both further the knowledge concerning the chemistry of degradation, and also to progress
towards a stage where these techniques were directly applicable to Cold Mill problems. From this
knowledge it was anticipated that standard methods could be proposed to test new rolling oils
without recourse to full scale trials.
4.b. 1. Degradation of Synthetic Esters and Rolling Oils

During use, rolling oils are known to degrade in two ways. Extreme pressures in the roll bite ensure
that hydrolytic ageing (oil used as an emulsion) takes place. Once plated out on the strip, rolling
oils are in good contact with both air and steel at elevated temperatures, leading to oxidative
ageing.
a. THE MECHANISM OF OXIDA TIVE AGEING
Samples of synthetic esters and rolling oil formulations were heated in an air oven at 80 C in open
petri dishes. On the surface of the samples a fine sprinkling of iron powder was made to act as the
catalyst.
During one set of experiments, the weights of the dishes were regularly taken. This led to the
profile seen in figure 25, all esters gaining weight. The maximum weight gain correlated well with
the degree of unsaturation of each ester. Following this maximum, a weight loss was seen as
degradation and loss of the subsequent volatile species occurred. Although this maximum occurred
at equivalent times for the synthetic esters, natural liquid glyceride degraded far more quickly,
suggesting that its replacement with synthetic esters in rolling oil formulations should lead to more
stable formulations. The same study for three oil formulations showed a consistent small weight
loss, anti-oxidants in the packages preventing oxidative ageing, weight loss being as a result of
distillation. All samples subsequently aged oxidatively in a laboratory were treated for a period of
72 hours. From this work it can be concluded that double bonds are active sites for oxidation,
formation of peroxides leading to subsequent fracture of the chain. The rapid oxidation for natural
tri-glycerides explains the statement made in the introduction, that glyceride behaved unexpectedly
in oxidation studies, being aged for the same duration as other oils in these earlier studies.
38
0.14
32 48 56 72
Hours of ageing
.TMPtristearate . NRG distearate __ Pentaerythritol tetraoleate
. NPG dioleate . Liquid glyceride
Figure 25 : Oxygen uptake during oxidative ageing
A study was made into the change in the ester chains in a number of esters using FAME (12) (Fatty
Acid Methyl Ester analysis) with GC-MS analysis. The synthetic esters were hydrolysed using
methanolic sodium hydroxide to give the parent acids, and these acids subsequently esterified using
boron trifluoride. Subsequent GC-MS analysis gave details concerning the changes to the ester
chain with oxidative ageing.
It was evident that for materials containing double bonds, degradation at the double bond to form
new species occurred, confirming the findings from gravimetric determinations. A shortening of the
carbon chain by 2 units was seen, despite the fact that the unsaturation normally occurred towards
the centre of the chain. This suggests that degradation is not simply by cleavage at the double
bond.
b. HYDROLYTIC AGEING
To age oils and esters in conditions similar to those occurring in the roll bite it was necessary to
use a device known as a bomb, able to withstand high pressures at elevated temperatures. A
mixture of 15 g oil, 15 ml of water and 1 g of iron fines was aged in an oven for 24 hours at
140C. The oil was then recovered from this emulsion in one of a number of methods. Each
method was assessed for its suitability for purpose.
39
The single disadvantage of rotary evaporation to recover oil from emulsion was the use of further
heating. Although the heating was moderate in comparison to that experienced during ageing, use
of FT-IR showed that further degradation occurred as a result of rotary evaporation on a water bath
at 70 C. A noticeable decrease in the quantity of esters in samples was seen for this work,
indicating further ageing had occurred.
Currently, the acid split method is the method used in many Cold Mill laboratories to give an
indication of the oil concentration in emulsion systems. Although simpler, faster and less expensive
than the rotary evaporation technique, there are drawbacks when used for surface cleanliness
studies. The more polar species formed due to degradation remain in the aqueous phase after the
separation has been effected. This is confirmed by comparison with rotary evaporated samples
using FT-IR analysis. Noticeable low recoveries are seen for fatty acids and materials containing
double bonds, active sites for subsequent degradation.
A rapid method based on SPf* 13 ' (Solid Phase Extraction) was employed to extract oils from the
aqueous mixture. This proved to be the quickest and simplest of the three methods.
When compared to the rotary evaporated samples by GC-MS, there appears to be complete
extraction. However, closer examination shows the absence of esters and acids, these polar species
being retained on the silica cartridge. For the purpose of surface cleanliness research studies, it is
not recommended that this method be utilised, although it shows excellent prospects for
quantifying oil concentrations in emulsion systems. Examination of the extracts using FT-IR showed
them to be in equivalent states to samples prepared by the acid-split method.
Interpretation of FAME (Fatty Acid Methyl Ester) analysis for hydrolytically aged samples showed
little difference in the ester chains from the unaged materials. This did not vary with the method
of oil extraction. It can therefore be concluded that any degradation of the ester chain is entirely
via oxidative mechanisms.
4.b.2. General Observations on Ageing of Oils and Esters
a. CHANGE IN POLARITY MEASURED BY SPE
It is assumed that any degradation of oils will lead to an increase in polarity of materials, either due
to incorporation of oxygen or addition of hydroxyl groups, followed by subsequent degradation.
40
Use of a silica SPE cartridge and
NPG dioleate Liqiid gtyceride Fifi formulation
100%
washing w i t h successively polar LJIMil
solvents allowed four fractions 80%
Q Polar
f r o m a sample t o be collected in 60%
increasing order of polarity (figure 40%

Nonpolar
26). NPG dioleate, liquid glyce
ride and a full formulation were
examined in varying aged states,

20%
0%
S : co
- III

<3>

O o . co
<
these three materials being selec a S 05
C
<2
^
< >
CC
T?

c 2 3 => 3 3
3
ted to cover synthetic esters, na
tural esters and the final package.
Figure 26 : SPE data showing change in polarity as a
result of ageing
NPG dioleate showed little change in polarity for oxidative ageing, although hydrolytic methods
appeared to produce greater quantities of both less and more polar fractions than the starting
material. In the case of the liquid glycerides, oxidative ageing had a more pronounced effect on
nonpolar species in the starting material from the data obtained. Hydrolytic ageing showed a
general increase in polarity, with rotary evaporation showing the biggest change. Interpretation of
the full formulation data suggests that the extraction from water is the only significant factor
altering polarity.
From these findings it can be concluded that removal of an oil from water is not perfect, further
degradation being seen as a result of rotary evaporation, and incomplete extraction by the acid split
route. For materials not containing antioxidants, once a certain point is reached, oxidation proceeds
at a significant rate. In the case of NPG dioleate that point had not been reached, whilst for
glycerides, nonpolar materials had been preferentially degraded. In the case of full formulations
which prove to be resistant to ageing, emulsifiers significantly hamper extraction of oil from
emulsions.
b. GPCANALYSI S
The same materials were analysed by GPC (Gel Permeation Chromatography), using the parameters
defined in appendix I. It was not possible to calibrate the column to give molecular weight
information, but the data was interpreted to identify whether changes to the starting material had
resulted in increased or decreased molecular size.
41
Once again, oxidative ageing for NPG di-oleate showed more change than for hydrolytic
degradation, a small quantity of larger species being evident at the expense of the starting material.
For liquid glycerides, a more complicated set of profiles were produced. Oxidative ageing did not
seem to generate large quantities of bulky species, but a significantly increased quantity of smaller
molecules. This anomaly may be due to the extent of oxidation for the glycerides, the maximum
point being surpassed by some way. It is likely that the precursors to oxidation have been further
reacted to generate a number of smaller, more polar compounds. This is in good agreement with
the SPE findings in the previous section. Hydrolytic ageing showed the results anticipated, new
materials being larger in size, especially for the sample prepared by rotary evaporation. Finally, the
rolling oil package showed no signs of polymerisation, the anti-oxidants working effectively.
c. FT-IR ANALYSIS
FT-IR spectra were obtained using a drop of oil on a KBr window, collecting signals between 750
and 4000 cm" 1 . Literature data ( 1 4 , ( 1 5 ) < 1 6 ) show that for oils a number of wavelengths are of
significance. The following regions have been measured semi-quantitativeiy for the aged oils and
esters.
Wavenumber / cm" 1 Functionality
3460.00 Hydroxyl
3030.00 Unsaturation
2860.00 CH 2
1780.00 Lactones
1740.00 Esters
1710.00 Ketones, aldehydes & acids
For all aged ester samples there is strong evidence for oxidation of the esters and double bonds.
These conclusions can be drawn from the decrease in both carbon-carbon double bonds and ester
peaks. Oxidative products from this degradation include lactones, ketones, aldehydes and organic
acids. Where few double bonds are present in the starting sample, less oxidation has taken place.
Hydrolysis has also occurred as can be seen by increase of the hydroxyl peak. Hydroxyl bonds have
a very strong infra-red absorbance, and although it may not appear that acids have been formed
from the C = 0 stretch frequency at 1710 cm" 1 , this increase in hydroxyl groups is probably as a
result of free fatty acid formation. Hydrolytically aged samples show larger acid and hydroxyl peaks
which agrees with the mechanisms expected as a result of heating in the presence of water.
42
Concerning the various methods of extraction of esters from emulsions, it can be seen that the
decrease in quantity of esters present is greater for the rotary evaporated samples than for those
prepared by other methods, indicating that further heating of the sample during rotary evaporation
has further degraded the sample. Reduction in the level of carbon-carbon double bonds is also
marginally greater for the acid split and SPE samples than for those prepared using rotary
evaporation.
As seen with other analyses in this project, full formulations proved to be resistant to degradation,
little change being observed between unaged and aged samples.
4.b.3. Degradation of Fatty Acids

A number of long chain saturated fatty acids were purchased and a known amount loaded onto
samples of solvent-washed hard iron in order to determine the interactions between the substrate
and analyte in order that correlations be made with rolling oil materials. XPS and FAB-SIMS analysis
was carried out using parameters defined in the method development section. XPS analysis of
untreated samples showed good agreement of elemental data with the empirical formulae. Further
analysis of the C 1s spectra also showed excellent agreement with the functionality of the acids.
These samples were also treated thermally by heating to 200C on a hot plate. A number of
unsaturated fatty acids of chain length C 1 6 to C 1 8 were also analysed using FAB-SIMS on a hard
iron substrate.
For the thermal treatment of myristic,

palmitic and stearic acids (0.01 g) over a
period of time, only stearic acid showed
a trend of chemical change (figure 27) -C14
.ce
with extent of ageing. Discolouration -C18
observations showed a trend for all

three acids, a gradual darkening of the
organics being seen. This suggests that 10 20
oxidative ageing of stearic acid can be Minutes aged
monitored with the technique of XPS, a

possible use being the identification of Figure 27 : Oxygen uptake for saturated fatty
acid ageing measured by XPS
severe oxidative ageing of oil on coils
stored at the pre-anneal stage of the process route.
43
Analysis of larger quantities of acids (0.04g) showed that the longer the C-chain of the acid, the
greater the levels of carbon remaining on the surface following heating. The mechanism put forward
for this work is on the same principle as work described earlier for oxidative ageing of esters.
Addition of oxygen at positions along the carbon chain results in an increase in oxygen levels
relative to carbon. Cracking of the chain, followed by release of the volatile component then results
in a drop in oxygen levels. These chains, once cracked, can then reform to produce polymers of the
starting materials.
FAB-SIMS analysis shows that ions indicative of the acid can be assigned and that subtle
differences in the fatty acid chemistry, such as the number of C = C bonds present can be
monitored. This is important, since it is evident that the presence of C = C bond in materials can act
as a reaction centre for degradation under thermal loading.
4.b.4. Analysis of Iron Decanoate

Metal soaps, particularly those containing iron, are known to be present in rolling oil emulsions.
They are believed to be formed from the reaction of free fatty acids, hydrolysed from synthetic
esters used in the rolling oil emulsion formulation, with the iron fines produced during strip rolling.
A sample of iron (III) decanoate, a possible model compound of these iron soaps, was obtained from
Fisons Chemicals and has been analysed using both XPS and FAB-SIMS.
A gold foil was cleaned by ultrasonic agitation in acetone and then dried using a hot air blower. Iron
decanoate was melted onto the cleaned gold foil, then spread into a thin film and allowed to cool
for approximately thirty minutes prior to analysis.
Quantified XPS elemental analysis (excluding gold) compares reasonably with that of the expected
empirical composition. The slight differences could be explained either by a small amount of Fe 2 0 3 ,
perhaps as an impurity in the iron decanoate, or a small amount of co-adsorbed water. The
deconvoluted C 1 s spectra revealed carbon to be present in two environments. On the basis of their
relative binding energy positions these peaks may be assigned as follows: the major peak was due
to the C-C / C- species which are present in the hydrocarbon portion of the decanoate molecule
and the other peak corresponded to the carboxylate C(0)0 groups bonded to iron. The 0 1 s
spectrum shows two components due to C(0)0 and Fe-0 species, while the iron 2p spectrum
shows only one peak, consistent with an Fe'"0 species.
44
The high resolution C-|S and 0 1 s spectra revealed the electronic environment of the carboxylate
group to be consistent with a delocalised structure and that the C-0 bonds are electronically
equivalent. The relative binding energy position of the C(0)0 moiety in the C 1 s spectrum (288.8
eV) suggests a covalent type of bonding with the iron centre, rather than an ionic interaction,
which might be expected to have been observed at a binding energy of 289.9 eV. This shows
that iron carboxylate compounds of fatty acids of C 1 0 and above are probably more covalent in
character than, for example, iron acetate. Therefore, any compounds formerly assigned to iron
carboxylates in the C 1s spectra during the current work on rolling oil surface chemistry may have
either been compounds of shorter chain fatty acids or have more electropositive metal ions, such
as sodium, potassium or calcium included their structure. Moreover, the assignments of peaks at
288.8 eV in the C 1s spectra may be due to long chain fatty acid esters or indeed iron carboxylate
derivatives of the corresponding acids.
The FAB-SIMS positive ion spectrum showed peaks at the following m/z values, which can be
readily assigned; 172, decanoic acid, 227, [Fe(C 10 H 19 O 2 )] + and 398, [Fe(Ci 0 H 19 O 2 ) 2 ] + . Fragment
ions of lower m/z (<200) were found to be more abundant than those at higher mass, consistent
with fragmentation of long chain hydrocarbons. The presence of an organosilicone impurity was
also observed, which may have been present in the lubricant used on the ground glass joints of
apparatus used in the preparation of the iron decanoate.
4.b. 5. Stepwise Ageing of Rolling Oils

A series of experiments were carried out Oxygen (250)
Nitrogen (250)
to determine the effects of burn-off Nitrogen (500)
atmosphere, oil coverage and tempera-
ture of a full formulation rolling oil. Oils
were sprayed onto Q-panels as a petro-
leum spirit solution to give coverages of
200(1) 300(1) 400(1) 500(1) 600(1) 600(2)
250 and 500 mg/m 2 . After allowing the Temperature deg.C (minutes held)
solvent to evaporate, coupons of a size
suitable for Leco determinations were Figure 28 : Influence of atmosphere and off coverage
cut and partial Leco determinations on carbon levels during Leco burn-off studies
measured by XPS
carried out on the Leco RC-412 under
either oxygen or nitrogen atmospheres. These involved raising the temperature to an upper limit for
a period of time as illustrated in figure 28, before removing the sample which was then analysed
by XPS. Table 6 shows the colouration of the samples following Leco treatment.
45
c 250 mg / m 2 500 mg / m 2 250 mg / m 2
(mins) under N ? under N ? under 0?
silver + somebrown silver silver + brown flecks

200(1)
flecks silver blue + brown spots
300(1)
light brown colour silver blue + brown dark grey / purple
400(1)
blue spots dark grey + brown
500(1)
purple blue / grey scale spots
600(1)
grey / blue brown / dark brown heavy grey scale
600 (2)
dark grey / blue heavy blue / grey scale v. heavy grey scale
Table 6 : Coloration of off samples on Q panels after Leco treatment
Elemental XPS determinations for C, Fe, O and Mn were made for each panel. In all but t w o
samples, there was little rolling oil residue visible on the surface. XPS revealed the presence of C
on the surface at a higher level than a panel undergoing the same heating process to which no oil
was applied. As the temperature increased for the low coverage sample under nitrogen, the carbon
level fell, due to desorption of the oil and the increased presence of FeO scale. A slight rise in
carbon at 500C was accompanied by the detection of metal carboxylates on the steel surface.
The same pattern was observed for equivalent samples under an oxygen atmosphere, with a more
marked contribution for FeO scale.
At higher oil film weights a different trend was observed. An initial slight increase in carbon from
200 to 300C was then followed by the reduction seen in the other samples. This then rose again
at 600C before dropping again when held for a longer period at this final temperature. This
behaviour could be indicative of a slightly more strongly bound rolling oil layer being formed, which
is richer in carbon. Evidence for such a layer was found in the form of metal carboxylates,
compounds which are known to bind strongly to the steel surface.
The data collected for the other elements were linked to the carbon profiles. Oxygen and iron
followed a reverse trend to the carbon. Manganese was detected in all samples, arising only from
the steel substrate. It diminished in concentration only when there was more carbonaceous material
or when FeO scale was formed on the surface.
For all samples, use of the C 1 s curve fitting algorithm showed several component peaks. As well
as signals due to C-C/C-H and esters, both present in the starting materials, ketones and metal
carboxylates. It is probable that ketones arise due to incomplete combustion of the hydrocarbon
chain via a peroxide, and that metal carboxylates as a result of interaction with the steel substrate.
It can be concluded that a high film coverage leads to species likely to have a detrimental effect
on steel surface cleanliness such as metal carboxylates.
46
4. b. 6. LECO Analysis of a Variety of Oil Types
During use it is likely that emulsion system may become contaminated with oils such as gear oil,
hydraulic oil and morgoils. These species are known to have a deleterious effect on subsequent
surface cleanliness levels. To date, surface carbon information obtained by Leco measurements of
hard iron have only reported total carbon figures, a qualitative description of the carbon source not
being given. With the newer Leco instrument, a study was carried out to ascertain the difference
in burn-off between a variety of oils.
A number of oils listed above were sprayed onto Q-panels to give a low coverage. Hard iron
samples from a post roll position were taken from two British Steel Cold Mills. The oils used are
different in both nature and pre-anneal residue concentration, although both deliver equivalent post
anneal surface carbon levels. All samples were analysed under the Leco RC-412 parameters
optimised in the method development work.
Comparison of the temperature profiles obtained for the tramp oils were markedly different from
each other and the two rolling oils, figure 29 shows the trace for a gear oil. A comparison is made
between the t w o different rolling oils examined here (figure 30). Although they appear to have
similarities in the peak positions, the areas of those peaks are different enough to allow the two
oils to be distinguished readily. It is interesting to note that the material rolling at higher plate-out
shows a bias towards the low temperature end of the burn-off profiles. When compared to the
lubricating oils, the morgoil, gear oil and hydraulic oil show a tendency to burn-off at elevated
temperatures, this being a likely reason for their poor performance when annealed.
Time /nominal units
Figure 29 : Leco burn-off profile for a gear oM
47
Time / nominal units
Figure 30 : Leco burn-off comparison for two rolling oils
From this work, it is clear to see that a method now exists for distinguishing between oils in their
neat forms. What is not yet clear is whether this method is capable of detecting contamination of
one oil by another, and at what level any contamination becomes determinable. Regarding new oil
formulations to be used on the mill, this Leco approach may be of use in assessing the burn-off
performance against the currently used product, before carrying out more time consuming annealing
trials, either in the laboratory or on a production scale.
4.b. 7. Analysis of Condensates from Laboratory Annealing Experiments

Laboratory annealing experiments carried out at Centre de Recherches Mtallurgiques (CRM)
investigating the influence of oil coverage, temperature, stress and oxygen injection generated a
number of condensates from this work. GC-MS apparatus was used to analyse both the
condensates in their neat forms and after clean-up using SPE to remove the mineral oil.
Analysis of the untreated oil in a hexane solution proved difficult to interpret due to the presence
of the mineral oil. The only conclusion that was reached here was that it was possible to distinguish
between steel annealed with normal oil concentrations, and those to which a quantity of oil had
been added. This conclusion was reached chiefly on the basis of an increase in size of the mineral
oil hump seen in the GC traces.
After successful clean-up by SPE, the traces became a lot clearer, as seen in the method
development phase for oil preparation. When compared to the starting oil, a number of new
compounds were present in the condensates, although only at trace levels, indicating that both
distillation and degradation of the oil had occurred during annealing. Mass spectrometry identified
48
these materials as being aldehydes, ketones, alkenes and lactones. The number of carbons ranged
from 8 to 12 and their structures were both straight chain (simple degradation) and cyclic
(indicating a rearrangement). Comparison of the quantities of these degradation products with the
annealing parameters led to the following trends.
Increased levels of degradation product are seen with excessive oiling and application of stress in
all cases. For samples with a high oil coverage, heating to high temperatures (700C) for sustained
periods of time seems to increase degradation, as does injection of oxygen. However, for samples
with normal oil coverage, the presence of oxygen makes little difference, other than when sustained
heating is used, in which case levels of degradation products in the condensate are reduced.
The formation of degradation products in the condensate is linked to the ease with which surface
oil can distil, both the application of stress and excess oil hampering this process. Under such
conditions the presence of oxygen creates combustion conditions rather than assisting in distillation
of the oil. To obtain a reduced level of degradation products, injection of oxygen in conjunction
with higher temperature anneals produces the following chemistry. Initially the oil distils, oxygen
playing no role in this, and at higher temperatures, the carboxylate species are combusted from the
surface rather than being 'cracked' in the inert annealing atmosphere.
4.b.8. Laboratory Annealing and Detailed Analysis of Steel and Condensates

A further set of limited experiments were carried out using the laboratory annealing furnace at
CRM, with a more detailed examination of both steel and condensates being implemented. Steel
was taken from a post rolling position from a working cold mill and samples prepared for laboratory
annealing. Annealing conditions were set to examine the influence of stress and temperature. Three
different temperature cycles were used, heating to 450C, heating to 700C and heating to 7O0C
with a hold at 450C.
The sample annealed without stress at 450C had more carbonaceous material on the surface than
the stressed material. However, the other unstressed samples showed less carbonaceous material
than their stressed counterparts. XPS C 1 s interpretations are given in Table 7. A similar level of
oxygenated material was seen for both samples heated to 450C, whilst at elevated temperatures
this increased for stress free samples. For both stressed and unstressed samples, the ratio of
oxygenated to non-oxygenated material decreased with extended thermal treatment. This is
indicative of increased oil removal and subsequent thermal degradation to give amorphous carbon.
49
C 1s component peak areas
Annealing Temperature
C(0)0 C-0 C(0) t o t C-C/C-H C(0):C-C/C-H
al
Without stress
Up to 450 C
88 271 359 1621 0.22
Up to 700 C
94 107 201 983 0.20
Up to 450 C (held) on to 700
76 151 227 1382 0.16
C
With stress
Up to 450 C
88 222 310 1304 0.24
Up to 700 C
79 115 194 1278 0.15
Up to 450 C (held) on to 700
65 79 144 1082 0.13
C
Table 7 : CI s data for laboratory annealed samples
Analysis of the condensates by GC-MS showed the presence of alkenes and cyclic compounds, as
well as the starting materials. There was no evidence for the presence of the other degradation
products reported in section 5.b.7., although the two rolling oils were not the same. From these
products, it appeared that degradation was more significant for stressed samples, and also for
those samples which were held at 450C for a period of time.
4.b.9. Investigation of Degradation with Excessive Off Levels

As detailed earlier in sections 4.b.5. and 4.b.6., excessive levels of oils on steel surfaces,
contribute significantly to formation of species consistent with poor surface cleanliness. Using
TDMS and XPS, determinations were made comparing hard iron having typically 100 mg/m 2 oil
coverage with the equivalent substrate having a coverage of 10,000 mg/m 2 . This involved heating
the steel to a temperature of 225 C for 40 minutes, before additional heating to a maximum
temperature of 580C for 10 minutes. XPS analysis was carried out on these materials
without atmospheric exposure, identifying the changes as a result of the heating. The samples
were also re-analysed by XPS after 2 weeks atmospheric exposure.
50
Prior to TDMS, the hard iron sample
showed three functionalities for the OC/OH
/
M
carbon, as determined by XPS. There C
3 /
was evidence for the presence of 2

hydrocarbon chains, ester and acid co
Standard oil coverage |

groups, consistent with the known 5
composition of an aged rolling oil. X^^j^r^y^^Â
Following TDMS experiments, a mar

Excessive oil coverage
l i l i l I
ked difference was seen, carbon
being present as a hydrocarbon com
Binding energy (eV)
ponent only (figure 31). Interpreta
tion of the Fe 2p region showed the Figure 31 : C1s traces for TDMS experiments varying
off coverage
iron to be converted from iron hy
droxide to the metallic iron as a result of TDMS, the material having a metallic lustre. Exposure to
the atmosphere resulted in a dramatic change, an increase in carbonaceous material being seen as
organics were adsorbed onto the surface, although these were still present at concentrations below
that of the original hard iron.
Studies with the doped material showed a different trend. Preexperiment analysis of the sample
indicated that the oil was consistent with an unaged material. A dramatic change was seen after
the TDMS experiment was completed, the yellow / brown residue being converted to a dark stain
in the centre of the sample, with a metallic lustre around the edges. The XPS survey spectrum was
dominated by carbon (figure 31), which was predominantly due to CC/CH species with a minor
contribution from C0 species. The iron spectrum showed an incompletely reduced surface, with
metallic iron being present alongside a small amount of hydrated iron oxide. After exposure to the
atmosphere the surface chemistry was altered to a more oxidised nature, although the level of
carbonaceous material was still high. This reduced the formation of an oxide layer.
From this work it is apparent that with a normal coating weight of rolling oil, thermal desorption
proceeds more rapidly than thermal degradation. However, more strongly adsorbed species are still
thermally degraded on the strip. Exposure to the atmosphere gives a hydrated iron oxide with some
metallic iron remaining.
5I
4.b. 10. Discussion of Laboratory Studies
a. MECHANISMS OF OIL AGEING
Studies into the mechanism of oxidative ageing has shown the importance of double bonds in the
formation of degradation products from the esters. Rolling oil packages proved to resistant to
laboratory ageing, the anti-oxidants functioning well. Gravimetric determinations, XPS measure
ments and FAME analysis all proved successful in linking the presence of double bonds to the
oxidative degradation of samples, with GPC showing polymerisation to be via an oxidative route.
Use of GPC and SPE analysis showed glycerides to be excessively aged, forming secondary
oxidation product which were both smaller in size and more polar than the starting materials. This
explain the previous anomalies with oxidative ageing described in the introduction section. FAME
determinations showed the reduction of carbon chains by 2 carbon units at a time, unsaturation
decreasing as ageing occurs. The use of FAB-SIMS can give a targeted analysis, identifying the
number and quantity of double bonds present in samples.
Hydrolytic ageing as a result of use in

| Secondary and tertiary products"| Ketone/Aldehyde
the presence of water was also asses
t \
Furan
Hydrocarbon
sed using a number of different techni Lactone
/ O-OH \
ques. Analysis of the effects of hydroly
j Hydroperoxides j Fk-CH-R. \
Hi. \ \
tic ageing was a little more uncertain
here, as the methods by which the oil
o
was extracted from water influenced the | Free fatty acid hydroperoxides | HO-OC-R
lEsterl / RrfM>R,
sample. FT-IR, GPC and SPE showing
that, whilst rotary evaporation recovered
more of the polar materials than the | Free fatty acids rto-c-
other methods tested, it also further

Fi ure 32 :
aged the samples. It is recommended 9 Degradation pathways for esters and oils
that unless materials of high polarity are

required, the SPE method developed by HOESCH113| be the standard method. FT-IR showed a
significant increase in the quantity of acids, ketones and lactones, linked with a reduction in the
ester peak as esters age. FAME analysis showed that the chain length of the hydrocarbon chain is
not affected by hydrolytic ageing, so it can be proposed that modification of chain length is by an
oxidative mechanism, with hydrolytic reactions occurring around the base alcohol. Once again,
rolling oil formulations proved resistant to change. The degradation routes for oils are summarised
in figure 32.
52
b. INFLUENCE OF OIL COVERAGE ON THERMAL DISTILLATION
Investigations into the influence of oil coverage on the degradation used a variety of experiments.
Stepwise ageing of steel panels, followed by subsequent XPS analysis showed that under normal
coverage, thermal distillation was the predominant mechanism for oil removal, although at higher
coverage thermal degradation became important. Evidence was found for the formation of metal
carboxylates under all conditions, this increasing with oil concentration. TDMS experiments
corroborated these findings, showing the formation of stains with extreme levels of oil. Analysis
of condensate from annealing experiments showed that under conditions in which oil cannot freely
move between steel panels, thermal degradation of the oils takes place. Condensation products
formed as a result of this included alkenes, aldehydes, lactones and ketones which were only
detected after using an SPE clean-up technique.
The ratio of oxygenated to non-oxygenated material, as determined by XPS, decreased with

extended thermal treatment. This is indicative of increased oil removal and subsequent thermal
degradation to give amorphous carbon. XPS and FAB-SIMS investigations into the nature of the
iron soaps showed iron decanoate to be a covalently bound species, iron soaps being likely
precursors to the formation of amorphous carbon.
c. IDENTIFICATION OF OILS OTHER THAN ROLLING OILS
Use of Leco apparatus has shown that it is easy to distinguish between rolling oils and tramp oils
in their neat states (figures 28 and 29). Work on material from two different plants has shown that
oil concentration alone does not define surface cleanliness performance, but the nature of the oil
and the temperatures at which it distils from the surface are major factors. It was shown that
surface carbon measurements can be used to predict which oils may lead to problems in annealing,
whether due to intentional use, or as a result of leaks in plant systems (tramp oils). Further
development is necessary to determine the levels of contamination which can be detected before
this can be implemented as a useful measurement.
D The laboratory research work commented on above was complemented by the plant
studies reported below.
4.b. 11. FAB-SIMS Analysis of Hard Iron

Development of FAB-SIMS techniques using proprietary chemicals in plentiful quantities gave data
concerning the ions which may be present on hard iron, components within the complex rolling oil
53
mixture being known. The ions previously observed from the TMP tristearate used in method
development were seen (tables A.I.3.A and B , appendix I), as well as a number of other acid
species. These ranged from length C 2 0 to C 1 6 and contained from 0 up to 3 double bonds.
Interpretation at higher m/z values is detailed in table 8. It is evident that this powerful technique,
coupled with careful interpretation, can prove invaluable in positively identifying rolling oil
components without recourse to removal.
Ion Count
Mass / Charge
Rate Assignment Comment
ratio
(Counts S"1)
TMPtriesters and fragments
[CgH, OaCOC, 7 H 3 5 ) 2 (COC 1 2 H

792 242 TMPtriester
765 209 25)1 + Fragment ions
751 203 Loss of (CH 2 ) 2 Fragment ions
709 203 Loss of (CH 2 ) 3 Fragment ions
Loss of (CH7)R
TMPdiesters and fragments
+
[C6Hu03{COC^7H35)2H]
666 126 TMPd ester
[C 6 H 1 1 0 3 (COC 1 7 H 3 5 )(COC 1 4 H 2
624 82 Fragment ions
P)H] +
Table 8 : FAB-SIMS analysis of high M/Z peaks of hard iron samples
4.b. 12. Tandem Miff Monitoring over a 30-day Period

It is known that the majority of surface residues leading to poor surface cleanliness are introduced
at the rolling stage via the emulsion system. Following renewal of the emulsion system as part of
the mill's routine maintenance, samples of emulsions, hard iron and postannealed steel were taken
to try to trace the buildup of products likely to have a detrimental effect on the final steel
cleanliness. The specification of the tandem mill is given in Tables 9. Emulsion samples were not
collected from tank 5, as this carried out only minimal reduction and also comprised a cleaner at
about 1.5 % (w/w), which was likely to have confused the analysis.
During this trial, there were no reports from Cold Mill staff that either the 5 stand was operating
in an unusual manner, or that surface cleanliness problems were experienced as a result of the cold
reduction process.
54
Stand 1 Stand 2 Stand 3 Stand 4 Stand 5
% Reduction of strip 35-44 25-30 20-25 18-22 1-1.5
Table 9.A : Stand details of tandem mill monitored
Tank 1 Tank 3 Tank 5
Supplies Stands 1&2 Stands 3&4 Stand 5
Volume (litres) 115,000 175,000 75,000

Oil (% w/w) 2.5-3.0 2.5-3.0 1.3 max
pH 6.0-7.5 6.0-7.5 6.0-7.5
Conductivity (pS cm"2) 150 150 150
Sap Value (mg KOH) 120-140 120-140 N/A
Iron concentration (ppm) 50 max 50 max 30 max
Chloride concentration (ppm) 10 max 10 max 10 max
Emulsion residence time (mins) 12-14 12-14 12-14
7ao/e 9.B : Emulsion tank details of tandem mill monitored
a. ROUTINE CHEMICAL ANALYSIS DATA
As part of the statistical process - 4 - . . Sap. value Stearic acid . -Oil(%)
control (SPC) procedures, chemi-

cal analyses are carried out each
shift on the emulsion systems,
ensuring that the parameters de-
tailed in Table 9b are maintained.
These data were tabulated during
the trial for correlation with other
v- CO I
analysis carried out as part of the

detailed assessment. The only
trend that was evident was a
Figure 33 : Variation of SAP value, stearic acid and oil %
slight decrease in the saponifica- during trial
tion values of both tanks towards
the end of the 30 day period. This is shown for tank 3 in figure 33, along "with the data for oil
content. During the trial, both oil content and saponification values of tank 1 were consistently
higher than those of tank 3, albeit by a small amount.
55
b. PARTICLE SIZE DISTRIBUTION ANAL YSIS
Use of the Malvern particle size instrument allowed particle size distributions to be obtained.
Following-on from the conclusions reached in appendix I, although speed of analysis was not
believed to be crucial to the accuracy of the determinations, samples were analysed the same day
where possible. For samples collected during the weekend, analysis was carried out with the
sample taken on Monday.
Because the data are presented as

a distribution, rather than figures,
without the aid of sophisticated
software and a good understan-
ding of particle size, much of the
data was not available for inter-
pretation. However, from data
giving the mean particle size and
the standard deviation around that
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29
mean, comparison was made bet-
Day of trial
ween the samples collected during
the trial. Careful examination of Figure 34 : Mean particle size of emulsion during monitoring
these data showed that for the
duration of the trial, there was no discernible variation in particle size distribution for either tank
studied (figure 34).
c. GC-MS ANALYSIS OF EXTRACTED EMULSION
Samples of emulsion were extracted using the rotary evaporation method, with subsequent
clean-up using SPE to remove mineral oil. At the completion of the trial, all samples were analysed
in a single batch, thus reducing the variability due to GC-MS performance.
Although no significant differences were seen for the extracted samples due to mineral oil, a trend
was observed for the samples after being cleaned up using SPE. When analysed semi-quantitatively,
stearic acid peak areas seemed to correlate with the saponification value (r = 0.76), but not with
the oil content (r = 0.04). This is shown graphically for tank 3 in figure 33. No trends were
apparent as a result of this, other than the drop in saponification value (and stearic acid) throughout
the trial.
56
d. LECO SURFACE CARBON ANALYSI S
The optimised parameters develo 800 -700

ped previously were employed for 700 / . - 600

analysis of hard iron samples ta | 600
/ - 500

ken during the plant monitoring | 500

o 400 J
5 400 o
trial. One of these was taken from
300 f
c
0 300 Am, 'Il ff
a coil processed during the start
c 200
1 200 Irf /// ft\ /111
of the campaign, whilst four
: - 100
~J*iJ \\//\y^ s?-*- &%
others were taken from the last 100
.0
third of the trial, figure 35 shows Time / nominal units
the burnoff profiles for these

Figure 35 : Leco burn-off profiles for hard iron during
samples.
plant monitoring
Samples of hard iron analysed gave surface carbon figures in the region of 100 mg/m 2 for organic
carbon and under 10 mg/m 2 for amorphous carbon. Comparison of the burnoff profiles obtained
showed little difference, peaks evolving at similar temperatures and in similar quantities. As with
the particle size distribution work, an algorithm is necessary to mathematically compare complex
data, that can only otherwise be compared visually.
e. SURFACE CHEMISTRY STUDIES OF HARD I RON
Analysis of the samples was carried out in the asreceived state and also after thermal ageing at
200 C as described earlier. Positive ion FABSIMS was also carried out for the asreceived samples
only.
320
High resolution C 1 s interpretations
are given in tables 10.a and 10.b
for the asreceived and thermally
treated samples respectively.
There is no discernible change
either in the asreceived samples
or in those that have been ther
mally treated. A full FAB SIMS 150 200 250
Mass Units
interpretation was made only for
the sample taken on day 1 of the Figure 36 : FAB-SI MS spectrum from hard kon sample
taken during trial
57
trial, other mass spectra being similar in appearance (figure 36). Ions were identified consistent with
acids ranging from C 2 0 to C 1 6 , with up to triply unsaturated acids for C 1 8 and C i 6 classes. These
were positively identified as the parent ion, pseudomolecular ion and ions resulting from loss of
water were seen for all acids. The interpretation for high m/z peaks was found to show both
TMP-triester and its fragment ions, and TMP-diester and its fragments.
Day of C(0)tota
C(0)0 C-0 C-C/C-H C(0):C-C/C-H
trial I
1 243 551 794 5552 0.14

21 208 482 690 5030 0.14
21 197 496 693 4669 0.15
29 200 475 675 5286 0.13
30 222 486 708 4865 0.15
Table 10.a : C1s data for as-received hard iron from trial
Day of C(0)tota
C{0)0 C-0 C-C/C-H C(0):C-C/C-H
trial I
1 243 543 786 5552 0.14

21 265 493 758 5030 0.15
21 248 475 723 4669 0.15
29 259 489 748 5286 0.14
30 269 452 721 4865 0.15
Table 10.b : C1s data for thermally treated hard iron from trial
f. XPS AND FAB-SIMS ANALYSIS OF EMULSIONS
Samples of emulsion and extracted oils taken on day 2 of the trial were analysed using surface
chemistry techniques. Extracted oils and emulsions were both prepared for analysis in the
as-received states and by thermal ageing at 200C. Due to degassing in the vacuum chamber of
the XPS instrument, it was not possible to analyse the thermally aged emulsion. A sample of hard
iron from the trial was also analysed.
58
Figure 37 shows the relative in As recewec gThernsSy treated
crease in C{0) area for the C 1 s 0.25
spectra for dried emulsions when

compared to hard iron, which
implies greater degradation of the
oil in the tanks. Emulsion taken
from tank 3 has the highest
C(0):C-C/C-H value, indicating
that it has undergone the greatest
amount of degradation. Extracted
Hari irem Bru!sicc3 extract 3
oil samples have slightly higher

C(O) values than the emulsion, Figure 37 : XPS data from hard iron, emulsionsand
further evidence of the role that extracted oils
rotary evaporation plays in sample
degradation. Analysis of the thermally treated materials showed that ageing of the hard iron had
the greatest effect. It was interesting to note that thermal degradation showed extract 1 to be more
degraded than extract 3, in contrast to both emulsion and extract analysis in the as-received state.
This suggests that thermal ageing may not be well controlled.
FAB-SIMS analysis of the dried emulsion provided a far more intense spectra than any earlier traces
recorder. As a result, not only were fatty acids from C 2 0 to C 1 6 seen, but as low as C 12 . A high
signal was also detected at m/z 134, the molecular mass of TMP. This is indicative of a degraded
emulsion, since samples of laboratory hydrolysed rolling oils have shown signals in this region.
Comparison of emulsions showed a higher relative intensity of unsaturated C 1 8 acids to stearic acid
than tank 1. Analysis of the extracted oils showed less peaks due to degradation products from
tank 1 in comparison to tank 3.
The mass spectra of the thermally treated samples show additional peaks due to fragment ions,
perhaps from polymerised groups formed as the degradation products of the long chain fatty acids.
There was also an increase in the levels of stearic acid, as a result of thermal treatment, probably
due to the further degradation of the base ester. A lower quantity of high molecular weight species
was detected after thermal treatment, corroborating the XPS work showing that degradation had
taken place during extraction.
59
4.b. 13. Conclusions from Plant Trial Data
Routine measurements showed tank 3 to have lower rolling oil levels than tank 1 . As the trial
progressed, a slight decrease was seen in the saponification values for both tanks. This trend was
also seen after rotary evaporation and SPE clean-up allowed stearic acid levels to be traced by
GC-MS. These correlated well with the saponification values obtained during the shift analysis.
Particle size distributions were not seen to vary, although the sensitivity of this method to small
changes is questionable. This is also the case for Leco RC412 surface carbon analysis. Both
techniques offer a wealth of information, but until computer algorithms can be developed to
improve on the basic interpretations used here, any slight changes will remain undetected.
High resolution C 1 s spectra collected during analysis of hard iron showed little change for any
samples, even after thermal treatment. Positive ion FAB-SIMS identified the presence of species
noted earlier, including acids and TMP species. There was no significant variation in these materials
during the trial. Similar studies using emulsion and extracted emulsions gave no indication of ageing
with use. Differences in C(O) to C-C/C-H ratios between extracted emulsions, the as-received
emulsions and hard iron showed tank 3 to be in a more degraded state than the first tank and also
the further degradation due to the extraction process. FAB-SIMS measurements showed the
presence of shorter acid chains for the emulsions, high intensity spectra being obtained. Evidence
backing up XPS data showing degradation during extraction was found, increased levels of
unsaturated C 1 8 acids occurring as high m/z intensities decreased, degradation of the base ester
being the cause.
The stability of the system under study ensured that there was insufficient variability to be detected
using current techniques. This is almost certainly as a result of the SPC practices that are in place,
continual small additions and alterations to the emulsions maintaining the required performance
criteria. In order to identify components of an emulsion which build up or decrease over time, that
have an effect of the steel surface cleanliness, a mill operating under less stringent conditions
would have to be selected for trials.
4.C. Discussion of British Steel Results
4.C. 1. Development of Suitable Methods

Use of SPE in subsequent analysis by techniques such as GC-MS gives a fast and selective
extraction of polar materials from an oil sample, eliminating mineral oil which often masks other
compounds of significance. These polar species are likely to be the materials of interest in surface
60
cleanliness studies, having a greater potential for chemical adsorption to the polar steel surface.
A single extraction can be carried out in under 5 minutes, at low cost and minimal solvent usage.
Another chromatographic technique, GPC was developed and the method used to detect the
presence of polymers in aged samples.
Development of the Leco RC412 operating conditions has allowed potentially informative data
concerning the burn-off of surface carbon from steel sheets to be assessed. Initial problems with
reproducibility have been overcome, with a complex temperature programme and use of an inert
atmosphere to prevent oxidation of residues. As well as gaining quantitative data, qualitative data
may be of use in identifying changes in an oil composition either as a result of degradation in use,
or as contamination of an emulsion system occurs. Use of the Leco apparatus has shown that it
is easy to distinguish between rolling oils and tramp oils in their neat states (figures 28 and 29).
Currently, the interpretation of the qualitative data is entirely visual, a mathematical or statistical
software program being needed to get the most from this technique.
Development of methods capable of analysing samples in-situ centred on XPS and FAB-SIMS
instruments. Use of high resolution spectra in XPS allowed carbonaceous material to be separated
into three classes; C(0)0, C-0 and C-C/C-H functionalities. This gave the possibility to compare the
extent of ageing of materials, high levels of oxygenated carbon relative to hydrocarbons likely to
indicate a higher degree of ageing. For other elements, O and Fe high resolution spectra could also
be obtained and used for interpretation. Use of thermal ageing of the samples at 200C
accentuated any differences in the samples.
FAB-SIMS complements this technique, giving positive compound identification. To assist

interpretation of the complex mass spectra, knowledge of species likely to be in the sample was
needed. With time and use, this technique is likely to be extremely useful in assessment of surface
residues. For instance, the degree of unsaturation of fatty acids can be determined. This is of key
importance in the degradation route, as will be discussed in 5.C.2.
Particle size determination methods for emulsions have been developed in the laboratory, Malvern
instrumentation proving considerably more suitable than image analysis equipment. Problems can
occur at high pump speeds, air being incorporated into the sample, giving rise to spurious peaks.
It is unclear how small a change in particle size distribution this method can' reliably detect, this
being its potential use in plant monitoring studies. As in the case of the Leco instrument, visual
and basic statistical interpretation do not obtain the full information available, the development of
improved data handling is likely to increase the usefulness of this technique.
61
4.C.2. Degradation Mechanisms for Oils and Esters
a. MECHANISM OF DEGRADATION OF OILS AND ESTERS IN SOLUTION
Studies into the mechanism of oxidative ageing has shown the importance of double bonds in the
formation of degradation products from the esters. Rolling oil packages proved to be resistant to
laboratory ageing, the anti-oxidants functioning well. Gravimetric determinations, XPS measure-
ments and FAME analysis all proved successful in linking the presence of double bonds to the
oxidative degradation of samples, with GPC showing polymerisation to be via an oxidative route.
Use of GPC and SPE analysis showed glycerides to be excessively aged, forming secondary
oxidation product which were both smaller in size and more polar than the starting materials. This
explains the previous anomalies with oxidative ageing described in the introduction section. FAME
determinations showed the reduction of carbon chains by 2 carbon units at a time, unsaturation
decreasing as ageing occurs.
Hydrolytic ageing, as a result of use in the presence of water, was also assessed using a number
of different techniques. Analysis of the effects of hydrolytic ageing was a little more uncertain here,
as the methods by which the oil was extracted from water influenced the sample. FT-IR, GPC and
SPE showing that whilst rotary evaporation recovered more of the polar materials than the other
methods tested, it also further aged the samples. It is recommended that, unless materials of high
polarity are required, the SPE method developed by HOESCH113) be adopted. FT-IR showed a
significant increase in the quantity of acids, ketones and lactones, linked with a reduction in the
ester peak as esters age. FAME analysis showed that the chain length of the hydrocarbon chain is
not affected by hydrolytic ageing. Once again, rolling oil formulations proved resistant to change
Surface chemistry techniques were used to analyse a number of the aged oils. In general, XPS
shows that there is a correlation between the C 1s and the 0-|S high resolution spectra observed for
most samples examined. Thermally aged oils showed an increased area due to C-0 species,
indicating that XPS can be used to give an indication of ageing. A notable change in the peaks
corresponding to the Fe 2p binding energies was also observed for the thermally treated (200C)
hydrolytically aged formulation, further evidence that the majority of metal complexes formed are
iron based.
Interpretation of the C 1 s spectra reveals an increase in oxidation for the majority of samples after
heating. Data from samples at 200C show that the full formulations have oxidised to a lesser
extent than samples free of additives. A number of samples showed evidence of metal
62
carboxylates. These species were found to be present in the full formulation and liquid glyceride
samples, but not in the those extracted from the emulsion. The absence of these species may be
due to the extraction procedure, carboxylates remaining in the aqueous layer. It was also interesting
to note that the NPG di-oleate samples were free of metal carboxylates, indicating that even
without additives, this is not easily hydrolysed. It can therefore be concluded that the XPS
technique has been developed sufficiently to provide details assisting in characterising an oil's
performance with regards to surface cleanliness.
TDMS and FAB-SIMS experiments were able to detect differences in the number of double bonds
in the fatty acids. Interpretation of the mass spectra from a limited number of thermally aged
samples showed a decrease in the number of unsaturated acids coupled to an increase in the
number of iron-organics with ageing.
From the interpretations listed here it can be proposed that for samples in liquid form, modification
of chain length is by an oxidative mechanism, with hydrolytic reactions occurring around the base
alcohol.. In the case of oxidative ageing, reaction to form degradation products centres on double
bonds in the ester chain. In the case of full formulation oil packages, these proved resistant to
change, the anti-oxidants functioning effectively.
b. MECHANISM OF DEGRADATION OF OILS AND RESIDUES ON THE STEEL SURFACE
Investigations into the influence of oil coverage on the degradation used a variety of experiments.
coverage thermal degradation became important. Evidence was found for the formation of metal
carboxylates under all conditions, this increasing with oil concentration. TDMS experiments
corroborated these findings, showing the formation of stains with extreme levels of oil.
The ratio of oxygenated to non-oxygenated material, as determined by XPS, decreased with

extended thermal treatment. This is indicative of increased oil removal and subsequent thermal
degradation to give amorphous carbon. XPS and FAB-SIMS investigations into the nature of the
iron soaps showed iron decanoate to be a covalently bound species, iron soaps being likely
precursors to the formation of amorphous carbon.
63
Analysis of condensate from annealing experiments showed that under conditions in which oil
cannot freely move between steel panels, thermal degradation of the oils takes place. Condensation
products formed as a result of this included alkenes, aldehydes, lactones and ketones which were
only detected after using an SPE clean-up technique. XPS determinations of the resultant steel
coupons showed that application of stress to samples gave increased levels of amorphous surface
carbon. For both stressed and unstressed samples, the ratio of oxygenated to non-oxygenated
material decreased with extended thermal treatment. This is indicative of increased oil removal and
subsequent thermal degradation of remaining residues to give amorphous carbon.
coverage thermal degradation became important. For steel samples that do not allow easy egress
for the distillates, such as stressed or high oil coverage, thermal cracking occurs, leading to species
such as alkenes, aldehydes, lactones and ketones. Collection of the distillate allows use of SPE in
combination with GC-MS to positively identify these materials.
4. c. 3. Development of Oil Performance Indicators

Work using Leco RC412 techniques on material from two different plants has shown that oil residue
concentration alone does not define surface cleanliness performance, but the nature of the oil and
the temperatures at which it distils from the surface is a major factor. It was shown that surface
carbon measurements can be used to predict which oils may lead to problems in annealing, whether
due to intentional use, or as a result of leaks in plant systems (tramp oils). Further development is
necessary to determine the levels of contamination which can be detected before this can be
implemented as a useful measurement.
Routine measurements showed tank 3 to have lower rolling oil levels than tank 1. As the trial
progressed, a slight decrease was seen in the saponification values for both tanks. This trend was
also seen after rotary evaporation and SPE clean-up allowed stearic acid concentrations to be
tracked by GC-MS. These correlated well with the saponification values obtained during the shift
analysis.
High resolution C 1 s spectra collected during analysis of hard iron showed little change for any
samples, even after thermal treatment. Similar studies using emulsion and extracted emulsions gave
no indication of ageing with use. Differences in C(O) to C-C/C-H ratios between extracted
emulsions, the as-received emulsions and hard iron showed tank 3 to be in a more degraded state
than the first tank and also the further degradation due to the extraction process. FAB-SIMS
64
measurements backed up XPS, data showing degradation during extraction, increased levels of
unsaturated C 1 8 acids occurring as high m/z intensities decreased, degradation of the base ester
being the cause.
The stability of the system under study ensured that there was insufficient variability to be detected
using current techniques. This is almost certainly as a result of the SPC practices that are in place,
continual small additions and alterations to the emulsions maintaining the required performance
criteria. In order to identify components of an emulsion which build up or decrease over time, that
have an effect of the steel surface cleanliness, a mill operating under less stringent conditions
would have to be selected for trials.
5. CONCLUSIONS
Batch-annealing heating-stage compressive stresses strongly increase rolling oil thermocracking,

by hampering the diffusion and free distillation of long molecular chains trapped in the inter-turn
species. This is particularly true under high gas flow conditions. These molecules remaining longer
at the surface degrade further, which increases the evolution of volatile gasses (CH 4 , C 2 H 4 ) and
the adherence of tar-like compounds obviously detrimental to final product cleanliness. The use of
100% H 2 protective atmospheres alleviates the problem, by favouring the formation of shorter
chains (hydrogenisation effect), and by increasing the fluxing of inter-turn spaces.
Technical procedures have been investigated to further eliminate oil residues from coil turn
interspaces, by acting on the thermocracking and gas-metal reactions which take place during batch
annealing. Research efforts were concentrated on evaluating the effects of stress relief procedures
based on modified heat cycles. They proved successful enough in terms of surface cleanliness, but
the isothermal holdings involved would strongly reduce productivity.
Another solution, consisting in evacuating the vessel, and carrying out the heating step under a
rough vacuum to promote oil distillation, was shown to provide only marginal improvement of the
final surface cleanliness. Although exploiting distinct reaction mechanisms, alternative procedures,
aimed at helping burn out undistilled oil residues and respectively based on water vapour and
oxygen injections, were seen to be efficient enough. They could however not be applied industrially
without proper optimisation, nor before some practical problems have been solved satisfactorily.
65
Finally, ultra-violet irradiation was used on cold rolled sheet steel specimens, in an attempt to break
chemical bonds in the surface oil residue molecules and induce their oxidation or peroxidation. The
benefit of cold rolled strip UV pretreatments on surface cleanliness after annealing under N 2 -5%H 2
looks far from satisfactory.
Two chromatographic methods of analysis were developed for application to rolling oils and
residues. The first, SPE, showed that changes in polarity could be detected and that, coupled with
GC-MS, components responsible for this could be identified. Formation of polymers was identified
by GPC, their presence likely to have a detrimental effect on surface cleanliness due to poor
burn-off characteristics.
In-situ methods of analysis were developed and applied. XPS was shown to give information
concerning the nature of the carbonaceous material, characterising a number of organics. This
technique was used throughout the project, giving information concerning the degree of
degradation, helping to build up an improved understanding of the mechanisms involved. It was
found that by thermally ageing samples at 200 C on a hotplate for 30 minutes, differences could
be accentuated. Positive identification of many species was possible using FAB-SIMS, with the
exact composition of free fatty acids being of vital importance for the ageing studies.
Degradation studies showed that modification of chain length is by an oxidative mechanism, with
hydrolytic reactions occurring around the base alcohol. In the case of oxidative ageing, reaction to
form degradation products centres on double bonds in the ester chain. In the case of full
formulation oil packages, these proved resistant to change, the anti-oxidants working well.
For oils on a steel substrate, XPS analysis showed that under normal coverage, thermal distillation
was the predominant mechanism for oil removal, although at higher coverage thermal degradation
became important. For steel samples that do not allow easy egress for the distillates, such as being
stressed or having high oil coverage, thermal cracking occurs, leading to species such as alkenes,
aldehydes, lactones and ketones. Collection of the distillate allows use of SPE in combination with
GC-MS to positively identify these materials.
Work using Leco RC412 techniques on material from two different plants has shown that oil residue
concentration alone does not define surface cleanliness performance, but the nature of the oil and
the temperatures at which it distils from the surface is a major factor. It was shown that surface
66
carbon measurements can be used to predict which oils may lead to problems in annealing, whether
due to intentional use, or as a result of leaks in plant systems. Further development is necessary
to determine the levels of contamination which can be detected before this can be implemented
as a useful measurement.
A series of experiments was carried out, monitoring the changes in an emulsion during use in order
to link certain chemistries to surface cleanliness. The stability of the system under study resulted
in insufficient variability to be detected using current techniques. This is almost certainly as a result
of the SPC practices that are in place, continual small additions and alterations to the emulsions
maintaining the required performance criteria.
67
6. REFERENCES
1. Analyse Chimique des huiles prsentes sur les tles d'acier, V. TUSSET, ECSC 7210/GD-
206, 1992
2. Verbessung der Sauberkeit von Feinblechoberflaschen, D. SOMMERS, ECSC 7210-KB/107,

1987
3. Relation entre la composition chimique des huiles de laminage et les rsidus organiques
surfaciques, P. DEWERBIER, La Revue de Mtallurgie-CIT, Mars 1992
4. The Effect on Cold Rolled and Annealed Sheet Surface Cleanliness of Steel Base
Composition, Particulate and Oil Residues Arising from Different Sources and Annealing,
R.H. JENKINS, ECSC 7210-KB/805, 1984
5. Ester Oxidation - The Effect of Iron, F. LOCKWELL, ASLE Trans., Vol. 25,2,236-244
6. Dveloppement de nouvellesmthodes d'analyse de composs organiques en surface des

produits sidrurgiques, H. HOCQUAUX, ECSC 7210-GD/309, 1990
7. New Techniques for Monitoring Chemical Changes in Rolling Oils which Affect Steel
Surface Cleanliness, M. CROSGROVE, CETAS Conference, May 1991
8. Raction gaz-mtal pendant le recuit-base sous hydrogne pur, L. BORDIGNON, ECSC Final
Report, 7210-KB/213 (D3/F22.89)
9. Influence des paramtres de recuit sur la raction gaz-mtal en bobines serres, B.

CHATELAIN, ECSC Final Report, 7210-KB/208, 1988
10. R. CRIEGEE, Chem. Uns. Zet., 5 75 (1973)
11. G.W. FABEL, S.M. COX, D. LICHTMAN, Photodesorption from 304 Stainless Steel, Surface
Science 40, 571-582 (1973)
12. Standard Methods for the Analysis of Oil, Fats and Derivatives, IUPAC, 1979, Method
2.3012, Section 3
13. D. SOMMER, Optimierung der Oberflacheneigneschaften von Feinblechen durch Einsatz

inovativer Walzolkonzepte, ECSC 7210-KB/116 (1/7/92-31/12/92)
14. F.R. van de VOORT et al., Monitoring the Oxidation of Edible Oils by FT-IR, JAOCS Vol. 7 1 ,
No. 3, p. 243
15. A. ALAN, J.E. NEWBERRY, Analysis of the Degree of Unsaturation in Edible Oils by FT-IR
Attenuation Total Reflectance, Spectroscopy 6 (1), 31-34, 1991
16. S.P.KOCHLAR, J.B. RUSSELL, Analysis of Oils and Fats using Infra-Red Specroscopy, Int.
Analyst., p. 23, Issue 5, 1987
68
APPENDIX I
A.1 METHOD DEVELOPMENT
During this method development, many of the oils and esters used have been thermally aged. A descrip
tion of the means by which this was achieved is given in section 5.b.1.
A.1.1 Use of Solid Phase Extraction (SPE) for Clean-up of Oils

The majority of species in rolling oil tend to be mineral oils. When analysed by Gas Chromatography -
Mass Spectrometry (GC-MS), the large 'hump' produced by the mineral oil components tend to obscure
a vast number of peaks eluting in the same region. The components under the mineral oil hump can often
be of interest in surface cleanliness studies, and at trace levels in the oil or residue under analysis. It is
therefore desirable to remove this mineral oil from the sample, whilst still retaining the other species.
A. 1.1.1. Experimental Details

Compounds making up the mineral oil tend to be non-polar in character, whilst the important materials as
regards surface cleanliness studies are significantly more polar, having a greater affinity for the steel
surface. SPE makes use of this range of polarity, effecting a separation as a pre-treatment step. The
sample of interest is dissolved in hexane (normally 0.5 g in 5 ml) and passed through an SPE cartridge
with a silica packing. Several 5 ml washes with hexane are made to flush the mineral oil from the cartridge.
The more polar species which are still bound to the cartridge are then removed using 2 ml of methanol.
GC-MS analysis was then carried out on a 25 m non-polar capillary column.
A.1.1.2 Results and Interpretation

Figures 3 a and b show typical examples of an oil treated in this way, acids being the evident species once
clean-up has taken place. This information would not be available without sample pre-treatment of this
kind. The method proved to be quick, simple to use and inexpensive.
A.1.2 Use of Gel Permeation Chromatography (GPC)

During use it is possible that oils may degrade to form polymers, species which will not easily be removed
from the steel surface during annealing, resulting in poor surface cleanliness. To monitor polymer
formation, GPC analysis was applied to the samples, using carefully defined parameters.
A.1.2.1 Experimental Details

A standard HPLC system was employed running under the following conditions. Samples were made up
as 0.1 g in 10 ml of toluene.
Column 30 cm 10 PL Gel
Mobile phase Toluene at 1 ml / minute
Injection Rheodyne 50 I loop
Detector Mass detector at 25 p.s.i. and 80 C
70
. 1.2.2 Results and Discussion
Peaks eluted within 10 minutes, evidence of polymerisation being seen for samples that had undergone
thermal treatment (figure 4). Repeatability was excellent and this method was later used to assist proposal
for reaction pathways for oils and esters.
A.1.3 Optimisation of Leco RC412 Surface Carbon Analyser Parameters

Surface carbon analyses have been carried out for a number of years using dedicated surface carbon
analysers. These instruments consist of a furnace in which a sample of steel is placed, through which a
stream of oxygen is passed. By choosing carefully selected temperatures for each of the two furnace
zones, certain classes of carbonaceous material combust in the oxygen atmosphere to form C02. This
is detected using a calibrated infra-red cell, giving a figure for the quantity of carbon liberated at the pre-set
temperature. It is normal for this application to set the front furnace zone at 350 C, reporting material
detected as organic carbon, and for the rear zone to be set at 600 C reported as amorphous carbon.
Although this standard technique generates useful information under routine conditions, no data is
generated concerning the nature of the organic carbon.
Newer instrumentation (Leco RC412 analyser) allows such information to be collected. Rather than a two
zone furnace being used, a furnace capable of being programmed accurately to cover a wide temperature
range (50 to 1200 C) is used, the other principles of operation remaining the same. In theory, this allows
a bum-off profile to be attained, showing how oils bum-off with temperature elevation. Another parameter
that can be altered is the combustion atmosphere, an inert atmosphere of nitrogen being available to act
as a distillation (as occurs during annealing) removal rather than combustion. It is these aspects of the
new device which will be important to surface cleanliness research, comparing oils for information on
burn-off performance, in a way that mimics annealing.
Initially, parameters were set to be as close to conventional two zone analysis as possible, a fast ramp
rate being used to gofrom350 to 600 C in an oxygen atmosphere, with long holds at both temperatures.
Although the figures generated for each phase were comparable to the old method, duplicate runs showed
there to be significant variation in the temperature profiles. Reducing the ramp rate did not improve
repeatability of the profiles, nor did starting analysis at reduced temperatures. It was felt that the quantity
of oil on the surface was hampering evolutionfromthe surface, possibly being further complicated by the
fact that removal was by a combination of oxidation (due to the oxygen atmosphere) and distillation. Use
of an inert atmosphere (nitrogen) gave very different profiles, and also improved repeatability of duplicate
analyses, although there was still some variation in profiles. The change in profile using the different
atmospheres is shown infigure5. It can be seen that this gives significantly more information, as further
peak resolution has been achieved. These conditions also improved the run to run reproducibility. The
optimised Leco RC 412 conditions are detailed in table A.1.1 and the effects shown in figure 6.
71
Ramp rate Temperature Hold
(C / min) (C) (mins)
1.00 100.00 1.00
2.00 50.00 120.00 1.00
3.00 50.00 250.00 3.00
4.00 50.00 270.00 3.00
5.00 50.00 300.00 1.00
6.00 50.00 350.00 2.00
7.00 50.00 650.00 6.00
Nitrogen supplied at 40 psi
Table A.1.1: Optimised parameters for Leco RC412
A.1.4 X-ray Photoelectron Spectroscopy (XPS) Experiments

The use of stripping of residues from the steel substrate for conventional analysis potentially leads to
alteration of the residues under examination. Surface cleanliness studies would therefore benefitfromuse
of an in-situ analytical method. XPS is a candidate for development.
Initially, instrument development work was carried out using laboratory prepared samples for which the
chemical composition was known. These included liquid glycerides (previously used in rolling oil formula-
tions), synthetic esters (currently used in rolling oil formulations) and the full formulations. Laboratory
ageing was employed to establish degradation via both oxidative (simulating oil being on hot strip steel)
and hydrolytic (simulating the rolling conditions) routes.
A.1.4.1 Sample Preparation

Due to the nature of the method, all oils analysed by XPS needed to be placed on a steel substrate. Initial
experiments used laboratory prepared panels (Q-panels grade R46) having a known and consistent
surface chemistry. A spot of sample was placed on the Q-panel prior to XPS analysis. A number of these
panels were heated on a hot-plate at either 150 or 200 C for 30 minutes to accentuate any differences
due to the chemistry of the oils. Table A.I.2 lists the samples analysed, the extent / method of ageing and
degree of subsequent heat treatment.
72
Elemental data C1s peak fitted areas
Atomic % relative to C-C/C-H
Temp
SAMPLES C
C O Fe Mn C(0)0 C-0 Total CO
Blank panels None 66.7 25.8 2.2 5.2 0.06 0.17 0.23
None 89.3 10.7 0 0 0.05 0.11 0.16

NPG dioleate, Unaged
150 78.8 20.9 0.3 0 0.14 0.25 0.39
200 74.4 25.3 0.4 0 0.18 0.23 0.41
None 87.0 12.4 0.6 0 0.05 0.10 0.15

NPG dioleate, Hydrolytically Aged
150 85.7 13.9 0.4 0 0.07 0.16 0.23
200 75.7 23.8 0.5 0 0.16 0.20 0.36
None 89.2 10.8 0 0 0.05 0.10 0.16

Glycerides, Unaged
150 79.0 20.8 0.3 0 0.15 0.25 0.39
200 74.7 25.0 0.2 0 0.18 0.27 0.45
None 86.8 13.2 0 0 0.07 0.21 0.28

Glycerides, Oxidatively Aged
150 79.3 20.3 0.3 0 0.13 0.22 0.35
200 78.9 20.9 0.2 0 0.15 0.24 0.38
None 86.1 12.9 1.0 0 0.04 0.10 0.14

Glycerides, Hydrolytically Aged
150 82.5 16.2 1.3 0 0.11 0.21 0.31
200 73.5 25.0 1.5 0 0.16 0.21 0.37
None 86.3 13.8 0 0 0.05 0.15 0.19

Full Formulation, Unaged
150 89.1 10.7 0.2 0 0.06 0.12 0.18
200 76.0 23.5 0.5 0 0.19 0.29 0.47
None 88.8 11.2 0 0 0.05 0.13 0.17

Full Formulation, Oxidatively Aged
150 89.1 10.7 0.2 0 0.06 0.14 0.20
200 75.9 23.8 0.3 0 0.16 0.21 0.37
Full Formulation, Hydrolytically Aged None 87.1 12.0 0.8 0.1 0.04 0.12 0.16
* 150 83.7 15.4 0.9 0 0.07 0.08 0.15
200 69.9 28.5 1.6 0 0.16 0.15 0.31
None 90.1 9.94 0 0 0.03 0.10 0.13

Oil from used emulsion (A)
150 88.9 11 0.2 0 0.05 0.12 0.17
200 89.2 10.6 0.2 0 0.05 0.11 0.16
None 89.8 10.2 0 0 0.04 0.11 0.15

Oil from used emulsion (B)
150 88.9 13.9 0.2 0 0.07 0.16 0.24
200 79 20.9 0.1 0 0.13 0.20 0.34
* Metal carboxylate detected
Table A.1.2: XPS analysis data for method development
A. 1.4.2 Survey Spectra

XPS data of the oils were collected with a VG ESCA 3 Mk II instrument using Al Kg radiation, 10 mA, 12
kV at ambient temperature and with a base vacuum pressure of between 10~7 and 10"8 mbar. Survey
spectra were carried out at a pass energy of 50 eV and high resolution spectra at 20 eV. The data were
analysed using SPECTRA, a computer based analysis package, together with literature valuesforbinding
energies. Oil samples were spread onto a small piece of Q-panel prior to analysis by XPS.
73
Table A.1.2 list the results of the as received, 150 C and 200 C thermally treated panels respectively.
Elemental determinations for iron, carbon, oxygen and manganese are totalled to 100% for this work.
Thermal treatment of the samples resulted in the formation of a brown colour on the steel surface, this
being more noticeable at higher temperatures.
A. 1.4.3 Peak Splitting for C 1s Spectra

Use of a computer curve fitting routine on the high resolution C 1s spectra, with literature binding energies
allowed the deconvolution of the C 1s peak to give four sets of peaks :
C-C/C-H from the carbon chain
C-0 from either an ester or an alcohol
C(0)0 from an ester or an acid
C(0)0-M from a metal carboxylate
These data are summarised in table A.I.2. The first three classes were present in all samples, but the
metal carboxylates were absent in all as received samples. It was possible to express the degree of
oxidation taking place with thermal loading, by comparing the signal due to C(0)tota, to that for C-C/C-H.
This ratio increased for the majority of thermally treated samples, the exceptions being the unaged and
hydrolytically aged full formulations treated at 150 C.
Peaks due to metal carboxylate in the C 1s spectrum were detected in four samples only, hydrolytically
aged liquid glyceride and fullformulationsat both treatment temperatures. The high resolution Fe 2p 3/2
peak for these samples displayed a noticeable shake-up satellite peak due to the phenomena of
metal-ligand charge transfer. This has been reported previously'10' for iron oxalate, and would therefore
be expected for iron carboxylates of fatty acids.
A.1.4.4 XPS Interpretation

In general there is a correlation between the C 1s and the O 1s high resolution spectra observed for most
samples. In comparison to the "as received" oils, there was a much larger area, and therefore concentra-
tion (table A.I.2), due to the C-O species, particularly at the binding energy peak positions corresponding
to the ester and metal carboxylate chemical shifts, thus the chemistry of the rolling oils could be observed
upon thermal ageing by in-situ XPS analysis of the C 1s and O 1s binding energies on the surface of the
steel substrate. A notable change in the peaks corresponding to the Fe 2p binding energies was also
observed for the thermally treated (200 C) hydrolytically aged formulation. However, there was no
significant change in the Mn 2p peaks. This is further evidence that the majority of metal complexes
formed are iron based.
Increases in levels of iron detected on the surface with thermal treatment may either be as a result of iron
carboxylates forming, or as a result of evaporation of C (as oil)fromthe surface, yielding a relatively high
74
iron / carbon signal. Therisein levels of oxygen for most samples with thermal treatment is indicative of
oxidation occurring at the surface of the steel, together with a decrease in the quantities of carbon being
detected. The exception to this was the hydrolytically aged full formulation treated at 150 C. This showed
a surprising increase in the level of carbon in comparison to other elements. Although performance of any
formulation containing radical scavengers should be expected to inhibit oxidation, an increase in carbon
would not normally be expected.
Interpretation of the C 1s spectra reveals an increase in oxidation for the majority of samples after heating.
Once again, the exceptions to this were the two hydrolytic samples discussed in the previous paragraph.
Although presence of anti-oxidants in the sample would explain this trend, the same would be expected
for the samples recoveredfromthe working emulsions. It is possible that the effects of the anti-oxidant
in the two emulsions taken from a working system have been overcome, oxidation having taken place.
Confirming this, data from samples at 200 C show that the full formulations have oxidised to a lesser
extent than samples free of additives.
Thermal treatment of the rolling oils resulted in the production of a discoloration on the surface of the steel,
which variedfromlight brown to black, depending on the extent of ageing, and showing up as differences
in carbon chemistry by XPS analysis. Hydrolytically aged oils gave rise to the darkest colours, stains being
of a similar nature to those found on steel after annealing. The liquid glyceride samples gave the worst
coloration, with evidence of metal carboxylates. These species were also found to be present in the full
formulation sample, but not in the two samples extractedfromthe emulsion. The absence of these species
may be due to the extraction procedure, carboxylates remaining in the aqueous layer. It was also
interesting to note that the NPG di-oleate samples were also free of metal carboxylates, indicating that
even without additives, this is not easily hydrolysed. However, an iron containing compound was detected
in the hydrolytically aged NPG di-oleate, although it was not a carboxylate.
Iron was detected in all thermally treated samples, but was only present before heating in hydrolytically
aged samples. This suggests that oils react with the steel only at elevated temperatures. The increase in
iron without an increase in manganese indicates possible iron oxidation or iron carboxylate formation,
although it is clear that not all iron goes to form carboxylates, these species only being present in four
samples. Therefore, some organic molecules must favour metal carboxylation over others, GC-MS being
a method(11) by which these can be identified. It is known that these are formed from acids, consequently
formation of carboxylates gives an indication as to the susceptibility of the base poly-alcohol esters to
hydrolysis.
A.1.5 Fast Atom Bombardment - Secondary Ion Mass Spectrometry (FAB-SIMS)

This technique is capable of yielding detailed information on steel surfaces concerning the identities of
75
chemical species present, as opposed to information on functionalities given by XPS techniques. To
ensure that the complex mass spectra generated during this analysis could be reliably interpreted,
methods needed to be developed in a stepwise manner, commencing with analysis of known materials.
A. 1.5.1 Experimental Parameters

FABSIMS was used in static mode, 4 kV Ar atoms primary beam at 1 nA. The instrument was used at
ambient temperature with a base pressure of 2 107 mbar. Initially, TMP tristearate was analysed in an
unaged format.
A. 1.5.2 I nterpretation of Spectra

Table A.I.3 describes the interpretation of the mass spectra for these materials. It can be seen that both
ions consistent with the presence of stearic acid and the TMP base can be seen for TMP tristearate
analysis.
m/z Assignment Comment
285 [M+H]+ Pseudomolecular ion stearic acid

284 [M]+ Molecular stearic acid
267 [C17H3sCOr Loss of water
251 [C^H^C]* Fragment ion
239 [C^Hgs]* Fragment on
Table A.I.3.A: FAB-SISM interpretation of ions indicative of stearic acid
273 [M(C8H17)]+ Fragment ion from TMP monostearate

245 [(C5H03)+(CO(CH2)7T [M(C10H21)]+
217 [(CsHÔaMCOiCHJaT [M(C12H25)r
189 [(CsHÔaMCOfCH^r [M(C14H29)]+
161 [(CsHÔaWCOH* [M(C16H33)]+
133 [(CsHÔaJ+Cr [M(C18H37)]+
119 [MH]+ Fragment ion from TMP
117 [MH2]+ Fragment ion from TMP
105 [C 4 H 9 0 3 r [M(CH3)]+
69 C4H9r [M(OH3)]+
Table A.I.3.B: FAB-SIMS interpretation of ions indicative of TMP species
A.1.6 Thermal Desorption Mass Spectrometry (TDMS) Development

A.1.6.1 Experimental Details
Preliminary thermal desorption work has been carried out for both unaged and hydrolytically aged NPG
76
di-oleate. These experiments were carried out in the analysis chamber of a VG Scientific SIMSLAB
instrument, using Electron Impact ionisation, with a VG Quadrupole Mass Spectrometer. Base pressure
was better then 109 mbar before commencement of the heating experiments.
A thin coating of the oil was spread onto a heatable molybdenum stub which was then introduced into the
analysis chamber of the VG SIMSLAB. Before heating, any volatile sample components were analysed
by mass spectrometry. Stub heating was then commenced and mass spectra were taken of the volatile
components over time as a function of increasing temperature. The volatile components were analysed
after electron impact (El) ionisation.
A. 1.6.2 Results and Interpretation

In all cases, there was no visible oil residues remaining on the surface of the stub, indicating that the oil
had desorbed completely. Mass spectrometric analysis of the sample stub after heating revealed that no
volatile organic components remained on the surface. Differences in the mass spectra of the unaged and
aged rolling oils were discernible at various temperatures. Results are summarised in table A.I.4,
according to the presence or absence offragmentationions from the Electron Impact (El) mass spectra.
No heating At 400 c
Unaged Aged Unaged Aged
746 [Fe(NPG di-oleate)]* X X

465 [Fe(NPG oleate)]* X X
352 [NPG(C14H2502)]* NPG my ristate / S /
337 [Fe (oleate)]* / X s
282 Oleic acid (C18:1) Free acid / X S
280 Linoleic acid (C 18:2) Hydrolysed once y X S X
278 Linolenic acid (C18:3) Hydrolysed twice s X y /
265 [C17H2902]* Linoleic acid - CH 3 s X X
178 [NPG]* Base alcohol s
Table A.1.4: Interpretation of mass spectra for NPG di-oleate
The fragment ions corresponding to the formula [Fe(NPG di-oleate)]+, [Fe(NPG oleate)]* and [Fe(oleate)]*
were detected in the hydrolytically aged sample only. A fragment ion was detected in both samples
corresponding to [NPG(C14H2502)]+, as well as the base alcohol, oleic and linolenic acids. The unaged
sample also showed evidence of linoleic acid and [C17H2902]* indicating loss of CH3 from linoleic acid.
A.1.7 Particle Size Analysis of Emulsions

A.2.7.1 Image Analysis Method Development
A drop of emulsion was placed under a cover slip before beingfocusedunder the microscope. A software
77
procedure was then used to calculate the feret average for each particle, and to give an average result
for the sample under the microscope. A feret is defined as a straight line measurement made between
tangents at various angles to the particle. The software used made 8 measurements (at 0, 22.5, 45,
67.5, 90, 112.5, 135 and 157.5 angles).
Problems in obtaining a well focused image on the screen were encountered, possibly resulting in errors
in measurement. Variations in particle sizefromsample to sample proved to be smaller than the standard
deviation for repeat analyses for single samples, making this approach of little use in obtaining accurate
information concerning changes in particle size. It is also doubtful that a single mean figure for a sample
allows subtle changes in a particle size distribution to be reliably detected.
A. 1.7.2 Malvern Mastersizer Measurements

A Malvern Mastersizer, operating on the principle of light refraction from the droplets in the emulsion, was
used to determine the particle size distribution of emulsion samples takenfroma working cold mill. After
shaking to homogenise the sample, a 2 ml aliquot of emulsion was placed in 500 ml of de-ionised water
and placed in the instrument operating at a pump speed of 2000 rpm. The refractive index parameter was
set at 4NAD with polydisperse analysis.
For a given sample, analysis was carried out 30 minutes after sample collection and at periods up to 5
hours after sampling to ascertain the importance of delay between sampling and analysis. A blender was
also usedforup to half an hour on 2 litres of emulsion to ensure a representative sample was presented
to the instrument.
Occassionally a quantity of material of larger particle size (>80 ) was evident in samples (figure 7). This
seemed to be independent of the sample, whatever the delay in sample to analysis time. Use of a blender
did not seem to alleviate this inconsistency in analysis. This phenomenon was even observed when a
sample previously analysed and found to befreeof larger particle size material was re-analysed without
being removed from the instrument. Variations in acquisition time within the loop did not improve the
consistency . Modifications to the pump speed, reducing it to 1500 rpm, minimised the levels of air being
incorporated into the samples, this being the cause of the sporadic peaks above 80 ..
A.1.7.3 Discussion of Particle Size Measurement Data

Of the two approaches, the Malvern instrument gave the most promising data. Problems with repeatability
for the image analyser limit its usefulness in detecting small changes, which may significantly effect rolling
performance. Despite problems of incorporation of air due to the mechanics of the Mastersizer,
reproducibility was good, both with time and from sample to sample. The emulsion system from which
samples were taken demonstrated good stability. Due to geographical limitations it was not possible to
78
present samples to either instrument in less than half an hour from sampling. It is therefore not possible
to categorically state that removal of a samplefromthe bulk does not give a 'true' particle size distribution.
79
European Commission
EUR 18634 Mechanical working (rolling)

Rolling oil distillation and thermocracking reactions in HNX and 100%
H2 annealing
M. Lamberigts, L. Bordignon
P. S. Legood
Luxembourg: Office for Official Publications of the European Communities
1999 79 pp. 21 29.7 cm
Technical steel research series
ISBN 92-828-5045-5
Price (excluding VAT) in Luxembourg: EUR 13.50
Steel surface cleanliness has been an important consideration for autobody grades for a
number of years. There is now, however, growing pressure to produce routinely clean
material for all grades via the batch anneal route, in order to compete with continuously
annealed material.
In this framework, CRM's first objective was to investigate the influence of the compressive
radial stresses building up between the inner turns of steel coils on oil degradation
mechanismus during batch annealing. For this purpose, a laboratory simulator was
developed to carry out annealing cycles on disk-like specimen stacks subjected to controlled
axial stresses. Although the latter led to an increase in the measured reaction gas evolutions
during simulation annealing cycles, the peak temperature of which had been purposely kept
below 400 C, they were shown to increase the total amount of carbon residue left on the
surface. This suggests that rolling oil degradation is reinforced by compressive stresses, thus
leading to higher levels of thermocracking and polymerisation. The use of pure hydrogen
protective atmospheres improves final surface cleanlines, presumably because of associated
higher rolling oil hydrognation and better gas fluxing.
In a second step, technical procedures were investigated to further eliminate oil residue from
coil turn interspaces, by acting on the thermocracking and gas-metal reactions.
Parallel to this, British Steel pic carried out degradation studies which showed that
modification of chain length is by an oxidative mechanism, with hydrolytic reactions
occurring around the base alcohol. In the case of oxidative ageing, reactions forming
degradation products centre on double bonds in the ester chain. Full formulation oil
packages proved resistant to change, the anti-oxidants working effectively.
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Rolling Oil Distillation and Thermocracking Reactions in HNX and 100% H2 Annealing

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E U R O P E A N

technical steel research

Mechanical working (rolling)

Rolling oil distillation

Contact: Mr H. J.-L. Martin

technical steel research

Rolling oil distillation and thermocracking

Cataloguing data can be found at the end of this publication.

Luxembourg: Office for Official Publications of the European Communities, 1999

European Communities, 1999

Reproduction is authorised provided the source is acknowledged.

PRINTED ON WHITE CHLORINE-FREE PAPER

RESULTS AND DISCUSSION 19

LABOFA TORY STUDIES

1. Degradation of Synthetic Esters and Rolling Oils 33

11. FAB-SIMS Analysis of Hard Iron 53

b. British Steel Contribution 66

Figure 1 : Batch-annealing simulator with stress application device

Figure 3: a) GC-MS trace of rotary evaporated oil extract from emulsion

b) GC-MS trace of SPE extract from previously extracted oil

Figure 4: GPC trace showing polymerisation of glyceride with ageing

Figure 5: LECO burn-off profile variation with atmosphere

Figure 6: Optimised LECO temperature ramp using nitrogen atmosphere

Figure 7: Particle size distribution of emulsion

Figure 8: Influence of compressive stresses on CH 4 evolution during annealing under 5% or

Figure 9: Influence of compressive stresses on surface cleanliness

Figure 25: Oxygen uptake during oxidative ageing

Figure 26: SPE data showing change in polarity as a result of ageing

studies measured by XPS

Figure 29: Leco burn-off profile for a gear oil

Figure 30: Leco burn-off comparison for t w o rolling oils

Figure 31 : C 1 s traces for TDMS experiments varying oil coverage

Figure 32: Degradation pathways for esters and oils

Figure 34: Mean particle size of emulsion during monitoring

Table 1 : Residual carbon pollution after heating to 400C (mg/m2)

Table 2: Efficiency of coil intertum compressive stress relief (T m a x = 400C, N 2 -5%H 2 )

Table 4 : Effect of oxygen injections on residual surface carbon

Table 5: Effect of a UV pretreatment on strip surface cleanliness

Table 6: Coloration of oil samples on Q panels after Leco treatment

Table 7: C 1 s data for laboratory annealed samples

Table 8: FAB-SIMS analysis of high M/Z peaks of hard iron samples

Table 9: a) Stand details of tandem mill monitored

b) C 1 s data for thermally treated herd iron from trial

Table A.1.1 : Optimised parameters for Leco RC412

Table A.1.2: XPS analysis data for method development

Table A.1.3: a) FAB-SIMS interpretation of ions indicative of stearic acid

Table A.1.4: Interpretation of mass spectra for NPG di-oleate

Consequently, subsequent carbon-removing gas-metal reactions (Boudouard and Fischer-Tropsch)

a) Further understanding the degradation of oils and esters;

3.a. CRM Contribution

Condensates, collected after various

room temperature are analysed conti- FURNACE 25 SAMPLES

cleanliness is assessed by organic re- 50 mm

Figure 1 : Batch-annealing simulator with stress

on surface cleanliness, based on

3.b. British Steel Contribution

Time>6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00

Figure 3. a : GC-MS trace of rotary evaporated off extract from emulsion

Figure 3. b : GC-MS trace of SPE extract from previously extracted oil

190 232 298 369 443 514 586 653 654

Figure 5 : LECO burn-off profile variation with atmosphere

Time / nominal units

Figure 6 : Optimised LECO temperature ramp using nitrogen

oc?;'''^' i ?SS3 ^ ? . ' ^ , r ' . J . g 8 S "Csa?:^'*??