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RESUMO
Prope-se um novo conceito de ao, no qual o cobre substitui o mangans na
estabilizao do enxofre. Este novo tipo de ao combina as vantagens tecnolgicas,
ambientais e econmicas da adio do cobre, com a possibilidade de reduo do
problema da fragilidade a quente. Portanto, tem grande potencial de utilizao em
estruturas soldadas e sujeitas corroso moderada, sem a necessidade de pintura.
A fundamentao tecnolgica da adio do cobre j bem conhecida, no que diz
respeito ao aumento das propriedades mecnicas pelo envelhecimento e melhoria
da resistncia corroso. Contudo, a fragilizao a quente sempre limitou a
fabricao deste ao por causa da formao de trincas no seu processamento a
quente. Este problema acaba por inviabilizar ou encarecer o produto por causa da
impossibilidade do uso de sucata contaminada com cobre ou do custo do nquel
adicionado para evit-lo. Resultados recentes indicam que a segregao do cobre
ocorre no entorno das incluses de MnS. Portanto, a fragilidade a quente pode ser
combatida de uma forma menos onerosa se o ao apresentar menos incluses, pois
a estabilizao do enxofre seria feita pela precipitao de CuS, que so mais finos.
Este trabalho prope uma nova forma de controle da fragilidade a quente pela
reduo ou eliminao total do mangans nos aos com cobre.
Palavras-chave: aos patinveis, fragilidade a quente, incluses, cobre, CuS
ABSTRACT
A novel concept of steels in which Cu replaces Mn in trapping the S is proposed. The
new steel combines the technological, environmental and economics advantages
resulting of the Cu addition, with the possibility of controlling the problem of the hot
shortness. As result, it has great potential use for welded unpainted weathering
structures. The improving of mechanical and impact properties by age hardening of
Cu containing steels is well know, and also its effect in preventing corrosion.
However, the problem of hot shortness increases the cost of production of the steel
because of the cracking during its hot processing by scrapping the plate or the
addition of Ni in preventing it. Recent results points that Cu segregates surrounding
MnS inclusions in steels. Then, the hot shortness can be prevented in a less
expensive way, by reducing the inclusions in the steel so the S is trapped by fine
CuS precipitation. This paper suggests a novel alternative solution for the problem of
the hot shortness by the partially or fully replacing of Mn by Cu in steels.
Key words: weathering steels, hot shortness, inclusions, copper, CuS
1
Contribuio Tcnica 64 Congresso Internacional da ABM - 2009 - Belo Horizonte MG
Brasil.
2
Departamento de Engenharia Mecnica da Universidade Federal do Esprito Santo,
Vitria, ES, Brasil comineli@npd.ufes.br
INTRODUO E JUSTIFICATIVA
As vantagens
Figura 2 - Corroso dos aos pintados, depois de 3 semanas em cmara de sal, 35C.
(1)
Da esquerda para a direita:(A36; A588; ASTM HPS 70W; NUCu).
Por causa disto, a sucata contaminada com cobre tem seu uso muito limitado e
acaba sendo descartada na natureza.
O problema
Fragilidade a quente
Por outro lado, o cobre tambm confere propriedades interessantes nos aos,
aumentando sua resistncia mecnica, resistncia corroso e resistncia ao
impacto, o que o torna um elemento importante na liga. Neste caso o problema de
trincas resolvido pela adio de nquel, que um metal caro.
FUNDAMENTAO CIENTFICA
sabido que o enxofre um elemento nocivo aos aos e deve ser controlado. O
enxofre residual (que no removido no processamento do ao lquido), pode
precipitar-se na forma FeS causando trincas durante o processamento a quente do
ao, devido ao seu baixo ponto-de-fuso. Para se evitar o problema adiciona se
mangans, de forma a estabilizar o enxofre que precipita na forma de incluses de
sulfeto de mangans (MnS) no interior do ao. Assim o problema causado pelo
enxofre fica resolvido. Resta ento o problema da fragilidade a quente causada pelo
cobre.
As pesquisas
file: 280025a
O fato de se produzir aos com maior teor de cobre e menor adio de elementos de
liga ir reduzir custos e conferir melhores propriedades mecnicas e de resistncia
corroso, possibilitando ainda a reduo de peso em estruturas e aumento de sua
vida til quanto corroso, podendo dispensar pintura. Estes aos so chamados
AOS PATINVEIS (WEATHERING STEELS) por serem empregados em
estruturas metlicas expostas ao tempo.
Uma dificuldade natural da total substituio do mangans pelo cobre est no fato
de praticamente no existir sucata livre de mangans e, neste caso haver
necessidade de adio de nquel. Aos totalmente livres de nquel tero ento que
ser produzidos a partir de novas corridas livres de mangans ou at mesmo de ferro
esponja.
CONCLUSO
A partir dos resultados experimentais e fundamentos tericos, fica claro que o fator
limitante da fabricao de aos com Cu a fragilidade a quente. Portanto, em se
resolvendo este problema, podemos desenvolver um ao patinvel com excelentes
propriedades, baixo custo e ecolgico, para aplicaes estruturais, a partir da
substituio parcial do Mn pelo Cu e melhor aproveitamento da sucata contaminada
com cobre. Numa primeira etapa, basicamente o objetivo investigar aos com
baixo Mn e Cu elevado, tendo em vista que praticamente no existe sucata livre de
mangans. Por causa do baixo Mn e da precipitao de enxofre como CuS, o ao
dever ter menos incluses e segregao de cobre no entorno delas. Tambm,
como o S estabilizado pelo Cu, a possibilidade de trincas a quente na soldagem
tambm ser controlada e a possibilidade de fragilidade a quente deve ser reduzida.
Posteriormente, numa segunda etapa, devero ser investigados aos totalmente
livres de mangans, produzidos a partir de minrios e matria-prima mais
selecionada.
Baseando-se na experincia acumulada com as pesquisas cientficas, duas novas
famlias de aos (aos contendo Cu, com baixo ou nenhum Mn) sero investigados,
de forma a se produzir aos com excelente combinao de valor tecnolgico,
comercial e ambiental, conforme abaixo:
Famlia 1) Aos Ecolgicos ou aos verdes: Aos contendo Cu produzidos a
partir de sucata contaminada com cobre. Estes aos tm um grande apelo ambiental
por causa da potencial melhoria nas propriedades advindas do aumento do uso de
sucata altamente contaminada, que seria inservvel na fabricao convencional. Pelo
fato de serem produzidos a partir de sucata, estes aos tero sempre algum Mn,
ainda que residual, e obviamente algum MnS. Portando eles devero ter problema
de fragilidade a quente e precisaro de alguma adio de Ni para evit-la. Estes
aos devem ter boas propriedades mecnicas, resistncia corroso e
soldabilidade.
Famlia 2) Aos com mdio e alto Cu, sem Mn Aos Comineli: produzidos a
partir de gusa livre de mangans ou do ferro esponja (reduo direta) que tem
tambm carbono muito baixo. Prev-se que eles tero menor problema de
fragilidade a quente no processamento, pelo fato de serem limpos de incluses. O
cobre neste caso far o papel de estabilizador do S na forma de CuS. Portanto,
pouco ou nenhum Ni ter que ser adicionado. Estes aos devero ter boa
combinao de custo, propriedades, resistncia corroso e excelente
soldabilidade.
AGRADECIMENTO
BIBLIOGRAFIA
1 VAYNMAN, S.; FINE, M. E. and BHAT, S. P. High Strength Copper Steel for
Rail Tank Cars to Bridges. Copper Applications in Metallurgy of Copper and
Copper Alloys, 2006.
Kinetics of the peritectic phase transformation: in-situ measurements and phase field
modeling. M. H. Phelan, D. J. Reid, and R. J. Dippenaar. (2006). Metallurgical and
Materials Transactions A, 37 (3), 985-994.
December 2006
Abstract
Development of higher strength-higher toughness steels for tank car applications has been a target for
many years to improve the overall performance of railroad tank cars. Over the past ten years, three
grades of low carbon copper-precipitation-hardened steels have been developed (NUCu-60, NUCu-70
and NUCu-100) in collaborative research between Northwestern University and Ispat-Inland Inc. The
two lower-strength grades are produced by air-cooling after hot rolling. The NUCu-60 Grade
(Supertough Cryogenic Steel) has yield stress of 415 MPa (60 ksi) and remarkable toughness at
cryogenic temperatures; more than 350 J (264 ft-lbs) down to 79C (110F). The NUCu-70 Grade
has at least 485 MPa (70 ksi) yield strength. Composition of NUCu-100 Grade is the same as that of
NUCu-70. The higher strength is achieved by quenching from the austenitizing temperature and aging.
The mechanical properties as well as the corrosion resistance and welding properties of these steels
are discussed. Finally, an update is provided on a recently built bridge using this alloy in Illinois.
Introduction
At the present time most of the tank-car shells are fabricated from 50 ksi-yield strength TC128B
carbon-manganese steel that contains more than 0.25% carbon and 1% manganese. This steel has a
relatively high carbon equivalent weldability parameter. In addition the steel has marginal fracture
toughness characteristics at low temperatures. A new more easily weldable, higher strength and
higher fracture toughness steel is sought for tank-car application. A series of high strength steels (as
described below) that satisfies these requirements was developed at Northwestern University. These
are excellent candidates for substitution of TC128B steel in tank car shell applications. These steels
have much lower carbon content. The strengthening is derived from copper precipitation on air-cooling
from hot rolling. Ni is added to prevent hot-shortness during hot rolling. Nb and Ti are added to control
grain size during hot rolling and welding. Since the NUCu steels are primarily ferritic, they dont
contain alloying to increase the hardenability. The initial investigations were done with laboratory
heats. Seven 45.4-kg laboratory heats of the steel were melted at Ispat-Inland R&D Department by
vacuum melting to work out the composition and processing conditions. Three more 135-kg laboratory
heats were melted at US Steel Company Research Center. To evaluate commercial steel production,
two 80,000-kg heats were produced at Oregon Steel Mills. One of the heats was used for rehabilitation
of a bridge in Illinois. Slabs cast at Oregon Steel Mills were also successfully hot rolled at US Steel
Corporation Gary Works. While some of the research results presented here were separately
1, 2, 3, 4, 5
published previously , this paper ties them together with previously unpublished results.
Higher steel strength makes possible the use of thinner sections to save weight. Significantly improved
weldability over high carbon steels should simplify and decrease the cost of fabrication. The 60 and 70
ksi versions of the steel are used in the hot rolled condition thereby saving the cost of normalizing.
High copper content gives significantly greater corrosion resistance, unpainted or painted, than usual
weathering steels thus minimizing tank car maintenance costs. The NUCu steels appear to be a cost-
effective alternative to the present steels used for tank car construction.
Results
Mechanical Properties
NUCu-60, as shown in Table I, contains higher Ti which ties up the interstitials. The NUCu-60 steel
heat was vacuum melted and hot-rolled into 0.5-inch-thick plates at Ispat Inland. The NUCu-70 and
NUCu-100-grade steels were cast at Oregon Steel Mills and hot rolled at US Steel Company Gary
Works. The composition is also given in Table I. While 70-80-ksi-yield stress was achieved in hot-
rolled and air-cooled steel plates up to 2-inch thick, water quenching and aging were needed to reach
100-ksi-yield stress. This paper describes the properties of NUCu-70 and NUCu-100 steels that were
cast at Oregon Steel Mills and then hot-rolled into 0.75 and 1-inch-thick plates at US Steel Company.
The NUCu-70 steel was tested in (a) as-rolled and (b) as-rolled and normalized at 900C. The NUCu-
100 steel was austenitized at 900C, water-quenched and then aged at 525C for 1 hr.
Round tensile specimens with a gauge section of 50.8 mm (2 inches) (ASTM E 8 Standard ) and
Charpy specimens (ASTM E 23 Standard) were machined in longitudinal direction from the quarter
thickness of the plates and tested. Multiple specimens were tested with very little variation observed.
The mechanical properties of the steels are listed in Table II. Table III shows Charpy absorbed impact
energy of steels.
Impact fracture testing of NUCu-60 steel shows its remarkable dynamic fracture toughness; Charpy
samples did not fracture down to -79C (-110F), they bent over in the Charpy apparatus as the
hammer swung through.
The NUCu-70 steel samples tested in as hot-rolled condition had yield stress of 503 MPa (73 ksi) and
UTS of 567 MPa (82 ksi). The elongation to failure is relatively high, 32% The Charpy absorbed
fracture energy fracture is also high, 161 J (118 ft-lbs) at -40C, this is much higher than required for
construction or tank-car application. Normalizing this steel at 900C increases the Charpy energy,
however reduces the yield to 461MPa (67 ksi) and UTS to 546 MPa (79 ksi). NUCu-70 steel more than
qualifies for use in tank-car construction in hot-rolled and air-cooled condition since the strength and
Charpy absorbed impact energy significantly exceed requirements for such application.
When NUCu steel of the 70 ksi yield strength grade was quenched from 900C and aged for 1 hr. at
525C the yield stress was increased to 712 MPa (103 ksi) and the UTS to 780 MPa (113 ksi) with
26% elongation to failure. The Charpy absorbed fracture energy is lower than that for NUCu-70 steel,
64 J (47 ft-lb) at -40C, an acceptable value for high-strength steel at this low temperature
Welding
Due to the very low carbon level and the absence of elements used to increase the hardenability such
as chromium and molybdenum NUCu steels have very low welding carbon equivalents. Figure 1
shows the Graville Diagram predicting weldability. Here the carbon concentration is plotted versus
carbon equivalent calculated as CE = C+(Mn+Si)/6 + (Ni+Cu)/15 + (Cr+Mo+V)/5. The Graville
Diagram is divided into three zones. In Zone I welds produced under most welding conditions are not
susceptible to cracking, in Zone II welding requires pre-heating and post-heating to prevent cracking
and in Zone III the heat-affected-zone (HAZ) is extremely susceptible to cracking. As evident from
Figure 1, NUCu steel having low carbon concentration and carbon equivalent is deep in Zone I and
thus does not require pre-heat and post-heat for welding, TC128B tank-car steel with its higher carbon
concentration and higher carbon equivalent falls into Zone II close to the border with Zone III indicating
difficulties in welding and susceptibility of HAZ to cracking.
Previously welding of several different heats of NUCu-70 steel was evaluated without pre-heat or post-
heat by a submerged arc (SAW) process and also by a manual process in a construction shop
environment (Trinity Bridge and Arlington Construction Companies). Matching consumables were
used. No brittle heat-affected zone was formed. Steel also was welded in a welding laboratory at
Northwestern University without pre-heat or post-heat using LINCOLWELD LA100 wire and
LINCOLNWELD 880M flux in SAW process. Two values of heat-input were used, 1.4 KJ/mm (35 kJ/in)
and 3.9 KJ/mm (98 kJ/in).
Table IV shows that the Charpy absorbed impact energies for welded specimens
including the heat affected zone are remarkable high for low heat input and
exceed the standard requirements for high heat input.
1.4 (35) 241 (176) 242 (177) 224 (164) 187 (137)
Duplicate G-BOP tests conducted at the U.S. Steel Research and Technology Center using a heat
input of 1.4 KJ/mm (35 KJ/inch) and low hydrogen AWS E7018 and E9018 electrodes without pre-heat
or post-heat did not show weld metal cracks in the welds or base plates.
Stupp Bridge Company, Bowling Green, Kentucky, recently performed a Procedure Qualification
(PQR) SAW Test without pre-heat and post-heat using Lincoln LA85 electrodes and MIL800-HPNi
flux. The heat input was 2.36 KJ/mm (60 KJ/inch). In fracture tests at -30C(-22F) the average
Charpy absorbed impact energy was 124 J (91 ft-lb). The requirement by the American Welding
Society Standard is 34 J (25 ft-lb) at this temperature.
Corrosion Resistance
6, 7
Copper significantly improves the corrosion resistance of steel in marine and inland environments ,
and the high copper content in NUCu steel is effective in substantially reducing the weight loss in
accelerated weathering tests.
Figure 2 compares the weight loss of NUCu steel to that for A36 steel and some weathering steels in
7
SAE J2334 standard accelerated tests performed at Bethlehem Steel Corporation by Townsend . The
thickness loss of A36 steel was133% greater than that of NUCu steel. The thickness losses of A588
weathering steels and HPS70W A709 steel were 69% larger than that of NUCu steel. Using existing
databases corrosion indexes have been established and the index for NUCu steel is far lower than
6, 7, 8
that for any other structural steel .
The same steel grades were coated with epoxy-based Carboguard 890 paint (Carboline Company),
9
scratched and then tested in a salt-fog chamber (D1654-92 Standard , 49.97 g/liter salt solution). The
extent of corrosion was measured after exposure at 35C for 3 weeks. Results of the tests are shown
in the Figure 3. The widths of the corroded regions adjacent to the scratches were measured and are
shown in Figure 4. Again NUCu steel demonstrates the best corrosion resistance; the corroded
surfaces at the scratches of A36, A588 and HPS 70W A709 steels were 93%, 52% and 54%
respectively wider than that of NUCu steel.
Summary
The information presented in this paper shows that NUCu 70 in particular has advantages over
TC128B steel presently used by the tank-car manufacturing industry. The higher strength should result
in weight saving. The higher impact fracture toughness mitigates against brittle failure particularly at
low temperatures. While the Cu and Ni alloying required increases steel cost, normalizing is not
required; NU-Cu steel is used in the as hot rolled condition. The much better weldability as indicated
by position on the Graville Diagram should significantly reduce fabrication costs. Pre-heat or post-heat
may be eliminated. The better weathering and corrosion resistance is also a plus. If outstanding
impact fracture resistance at very low temperatures is a factor, Supertough NUCu 60 is a candidate.
For still higher strength applications NUCu 100 may be the alloy of choice.
Bridge Application
The Illinois Department of Transportation (IDOT) recently announced the completion of a new bridge
in Lake Villa, Lake County (Illinois), constructed with a groundbreaking type of high-performance steel
developed by engineering researchers at Northwestern University.
About 500 tons of the copper alloy steel, known as ASTM A 710 Grade B high-performance structural
steel, was used in constructing the 430-foot span that carries the Illinois Rt. 83 over the Canadian
National Railroad tracks. IDOT is excited about the possibilities presented by this new type of cost-
efficient, high-performance steel developed right here in Illinois, said IDOT Secretary Timothy W.
Martin. Not only is this steel strong, tough and easy to fabricate, but it withstands the elements better
than typical steel, meaning it doesn't have to be painted. This makes construction easier and will
significantly reduce long-term maintenance costs.
IDOT is in the process of applying to the American Society for Testing and Materials (ASTM) and the
American Association of State Highway and Transportation Officials (AASHTO) to have this steel
designated as standard for bridge construction. The only previous use was in the rehabilitation of the
Poplar St. Bridge over the Mississippi River in the Metro East area.
The steel has a strength of 70,000 pounds per square inch (psi) compared with 50,000 psi in
commonly used structural steel. It is also easy to weld, and tests have shown it has high-impact
toughness at low temperatures. In addition, the high copper content gives the alloy much better
resistance to atmospheric corrosion than other high-performance steels.
We developed this steel nine years ago and application has been a long time in coming, said Morris
E. Fine, professor emeritus of materials science and engineering at Northwestern University, who
developed the new alloy with his colleague Research Professor Semyon Vaynman and with key
support from Northwestern's Infrastructure Technology Institute (ITI). This steel is cost-effective
because its processing is cheaper than competing structural steels of the same strength, its
weathering resistance is best, and it's easier to weld.
We are delighted to see our steel used in this new bridge and hope that the steel will be used in other
bridges in Illinois as well as in other states, said Vaynman, research professor of materials science
and engineering at Northwestern.
For more than a half-century, Professor Fine has been one of the seminal leaders in materials
science engineering worldwide, said David Schulz, director of ITI. The Infrastructure Technology
Institute is pleased and proud to have supported his team's development of the high-strength steel
employed in the Route 83 bridge. We look forward to continuing to help him 'push the envelope' of
ever-stronger and more economical steels.
The Lake Villa bridge was constructed by Dunnet Bay Co. with a contract value of $5.75 million. The
bridge designer was Graef Schloemer and Associates of Chicago. The steel was produced by Mittal
Steel USA in Coatesville (Pennsylvania), and fabricated at Industrial Steel Construction in Gary
(Indiana). IDOT received federal funds to pay for the steel through the Federal Innovative Bridge
Research Fund.
The project was supervised for IDOT by Resident Engineer Mario Biondolillo. Also playing a key role
for IDOT on the project was Chris Hahin, the principal investigator and metallurgical engineer for the
department. IDOT estimates not having to paint the steel saved $300,000. The new bridge replaced a
structure dating from 1929. Construction was carried out in stages in order to keep traffic flowing on
Rt. 83.
Authors
Prof. S. Vaynman and Prof. M. E. Fine: Department of Materials Science and Engineering,
Northwestern University, 2220 Campus Drive, Evanston, IL 60208-3108.
S. P. Bhat: Ispat-Inland, Ispat Inland R&D Department, 3001 East Columbus Drive, East Chicago, IN
46312.
References
1. M. E. Fine et al., International Symposium on Low Carbon Steels for 90's (Cincinnati, OH, ASM
International, 1993), 511.
2. S. Vaynman et al., Materials for the New Millennium, Proceedings of the Fourth Materials
Engineering Conference (New York, NY, ASCE, 1996), 1551.
3. S. Vaynman, I. Uslander, and M. E. Fine, Proceedings of 39th Mechanical Working and Steel
Processing Conference (Indianapolis, IN, ISS, 1997), 1183.
5. S. Vaynman et al., Microalloyed Steels 2002 (Chicago, IL, ASM International, 2002), 43.
8. ASTM G 101-01 Standard for Estimating the Atmospheric Corrosion Resistance of Low-Alloy
Steels.
9. ASTM D 1654-92 Standard Test Method for Evaluation of Painted or Coated Specimens.
http://www.fhwa.dot.gov/bridge/guide02.htm#1
C Mn P S Si Cu Ni Cr Mo V Al N
Old 70W * Min. - 0.8 - - 0.25 0.2 - 0.4 - 0.02 -
Max. 0.19 1.35 0.035 0.04 0.65 0.4 0.5 0.7 - 0.1 -
HPS 70W & HPS 50W Min. - 1.1 - - 0.3 0.25 0.25 0.45 0.02 0.04 0.01
Max. 0.11 1.35 0.02 0.006 0.5 0.4 0.4 0.7 0.08 0.08 0.04 0.015
* The conventional ASTM and AASHTO 70W grade steel has been replaced by HPS 70W
grade steel.
A36 0.3 %C; 1% Mn; 0.3%Si;
The theory behind all of this is that slightly misfitting coherent nanoscale precipitates locally lower
the Peierls stress of screw dislocations in iron. Steel has a ductile to brittle transformation because
the screw dislocations have a high Peierls stress. Thermal energy is sufficient at room temperature
so the screw dislocations are mobile but not at low temperatures. This causes the flow stress to
approach or exceed the fracture stress. It turns out that the metastable Cu alloy bcc cluster type
precipitates contain Fe, Mn, Ni etc. Ti ties up the interstitials thereby raising the fracture stress.