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Rolling oil distillation and thermocracking reactions in HNX and 100% H2 annealing

86 pages
Industrial research and development
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technical steel research
Mechanical working (rolling)
Rolling oil distillation
and thermocracking
reactions in HNX and
100% H2 annealing
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
Rue Ernest Solvay 11
B-4000 Liège
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
Science, Research and Development
Neither the European Commission nor any person acting on behalf of the Commission
is responsible for the use which might be made of the following information.
A great deal of additional information on the European Union is available on the Internet.
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
a. CRM Contribution 14
b. British Steel Contribution 15
a. CRM Contribution ig
1. Oil Distillation Mechanism -j
2. Surface Cleanliness Improvement 26
a. Compressive Stress Control7
b. Vessel Evacuation
c. Oxygen Injection8
d. Ultra-violet Irradiation 34
b. British Steel Contribution
1. Degradation of Synthetic Esters and Rolling Oils 33
a. The Mechanism of Oxidative Ageing
b. Hydrolytic Ageingg
2. General Observations on Ageing of Oils and Esters 40
a. Change in Polarity Measured by SPE9
b. GPC Analysis 4I
c. FT-IRs2
3. Degradation of Fatty Acids3
4. Analysis of Iron Decanoate4
5. Stepwise Ageing of Rolling Oils5
6. Leco Analysis of a Variety of Oil Types7
7. Analysis of Condensates from Laboratory Annealing Experiments 4
8. Laboratory Annealing and Detailed Analysis of Steel Condensates 4g
9. Investigation of Degradation with Excessive Oil Levels 50
10. Discussion of Laboratory Studies 5
a. Mechanisms of Oils Ageing
b. Influence of Oil Coverage on Thermal Distillation
c. Identification of Oil Esters other than Rolling Oils3 PLANT STUDIES
11. FAB-SIMS Analysis of Hard Iron 53
12. Tandem Mill Monitoring over a 30-day Period4
a. Routine Chemical Analysis Data5
b. Particle Size Distribution Analysis6
c. GC-MS Analysis of Extracted Emulsion
d. Leco Surface Carbon Analysis7
e. Surface Chemistry Studies of Hard Iron
f. XPS and FAB-SIMS Analysis of Emulsions 58
13. Conclusions of Plant Trial Data 60
c. Discussion of British Steel Results
1. Development of Suitable Methods
2. Degradation Mechanisms for Oils and Esters2
a. Mechanism of Degradation of Oils and Esters in Solution 6
b. Mechanism ofn of Oils and Residues on the
Steel Surface3
3. Development of Oil Performance Indicators4
a. CRM Contribution
b. British Steel Contribution6
Figure 1 : Batch-annealing simulator with stress application device
Figure 2:g 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 CH4 evolution during annealing under 5% or
100% H2
Figure 9: Influence of compressive stresses on surface cleanliness
Figure 10: Effect of stress level on gas evolutions during simulation batch-annealing (400°C)
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
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
700°C under N2-5%H2
Figure 16: Gas evolutions during stress-free batch annealing simulation No. 119 carried out to
700°C under N2-5%H2, 02 being injected between 400°C and 500°C
Figure 17: Gas evolutions during stress-free batch annealing simulation No. 109 carried out
under N2-21 %02 to 450°C and under N2-5%H2 from 450°C to 700°C
Figure 18: Gas evolutions during stress-free batch annealing simulation No. 136 carried out to
700°C (4-hour soaking) under N2-5%H2, 02 being injected between 400°C and
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 450°C under a) N2-5%H2, b) N2-5%H2
up to 350°C and N2-21 %02 over 350°C, and c) N2-21 %02
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
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 two rolling oils
Figure 31 : C1s 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 400°C (mg/m2)
Table 2: Efficiency of coil intertum compressive stress relief (Tmax = 400°C, N2-5%H2)
Table 3: Residual carbon surface pollution after annealing at 400°C under N2-5%H2 (15
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: C1s 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) C1s 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)Sn of ionse of TMP species
Table A.1.4: Interpretation of mass spectra for NPG di-oleate