Chemical and Physical Properties of Fluxes For SAW of Low-Carbon Steels
Chemical and Physical Properties of Fluxes For SAW of Low-Carbon Steels
Chemical and Physical Properties of Fluxes For SAW of Low-Carbon Steels
1. Introduction
The submerged-arc welding of steels has been used since 1930. It is well known that the
mechanical properties of steel weldments depend on the chemical compositions of
electrodes and fluxes. The development of welding electrodes has been based on practical
experiences. The study of welding deposits by means of physical metallurgy permitted to
develop electrodes and fluxes for SAW process of steels. In contrast, the use of chemical and
physical properties of fluxes for the development of welding process started in the 70´s.
(Shah, 1986). Most of the works concerning with the fluxes for SAW process have been
focused on its effect on microstructure and mechanical properties. Likewise, it has been
interesting the study of the thermochemical and electrochemical reactions that occur at the
welding pool which are very important for the transferring of metallic elements to the
welds. In addition to the stated above, the electrode coverings is also a very important
aspect to obtain weld metal with good mechanical properties. The covering materials are
fluxes which are composed of different mineral chemical compounds such as, oxides,
fluorides and carbonates (Singer & Singer, 1979). The firing and sintering process of fluxes
during welding electrode processing promotes chemical reactions and phase
transformations of these minerals. All these factors determine the valence or electric charge
of the different elements which are deposited to the weld metal. All the oxides from flux
may contribute to the dissolution process of different metallic elements and oxygen in the
welding pool. These metallic elements can react with oxygen to form oxide inclusions which
can serve as nucleation sites for the formation of some benefit phases such as acicular ferrite
during the welding process (Davis & Bailey 1991). These events may improve the
mechanical strength and ductility of weld metal. Thus, the purpose of this chapter is to
show the effect of different fluxes on the chemical composition, microstructure and
mechanical properties of weld metals by the submerged-arc welding procedure.
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282 Arc Welding
agglomerated from 400 to 900 o C and sintered from 1000 to 1100 o C from mineral
constituents, (Jackson, 1982). Reactions, which occur during firing of a ceramic oxide,
comprise phase transformations of minerals (Singer, 1963), reaction among the different
phases (Allen, 1966), formation of crystal phases from the melt and formation of a melt. The
phase transformation of the crystal phases predominates at the early stages of firing, before
a melt is formed. The formation of a melt can be observed at temperatures as low as 920 oC,
due to the presence of minor amounts of impurities such as, alkaline earth oxides (Dunham
& Christian, 1984). In this way, the agglomerated fluxes can be studied by the chemical
analysis of the crystal phases formed during the increase of temperature. This enables us to
quantify types of ions and their distribution, which is useful to predict their behavior when
they are dissociated in the submerged-arc welding process, (Indacochea et al., 1989). Thus,
this section shows a study of the crystalline phases and the chemical characterization of the
ions formed in agglomerated fluxes using Chemical Analysis, X-Ray Diffraction (XRD) and
Differential Thermal Analysis (DTA). It is also intended to show the effect of ion content of
flux on the behavior of submerged-arc welding.
crushed and then screened to a 240 m size. For comparison, a commercial agglomerated
200 oC for 24 hours, fired for 3 hours. at 950 oC in a gas kiln at a heating rate of 50 oC/h,
welding flux was also used, designated as T sample. The chemical analysis was determined
by X-ray fluorescence. The XRD analysis was conducted in a diffractometer with a
monochromated Cu K radiation. For all the samples, the DTA analysis was carried out in a
Al2O3 crucible from 25 to 1350oC at a heating rate of 10oC/min. Alumina was used as
standard reference for DTA analysis.
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Chemical and Physical Properties of Fluxes for SAW of Low-Carbon Steels 283
In the SAW process, the temperature of electric arc causes the dissociation of oxides and
these remains as ions in the plasma, (Belton et al. 1963). The temperature in the welding pool
reaches 1560-2300 °C. Christensen and Gjermundsen, (Christensen & Gjermundsen, 1962)
calculated temperatures above 2500 °C for the welding pool in mild steels. Apold (Apold,
1962) suggested that the heat energy provided by the electric arc is concentrated on a
circumference of 5mm diameter. According to the above information, most of the oxides are
melted, but oxides with high melting points such as MgO (2500-2800 °C), CaO (2572 °C) and
ZrO2 (2720 °C) are not melted. That is, it is important that the chemical formulation of fluxes
enables all the oxides to be melted in order to avoid the presence of inclusion in the
weldment.
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284 Arc Welding
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Chemical and Physical Properties of Fluxes for SAW of Low-Carbon Steels 285
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286 Arc Welding
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Chemical and Physical Properties of Fluxes for SAW of Low-Carbon Steels 287
Name Composition A B C T
Corundum Al2O3 9.17 17.90 12.11 19.07
Quartz SiO2 51.10 17.05 18.38 6.90
Nepheline NaAlSiO4 12.65 19.95 17.12 -----
CaAl2Si2O8.4
Gismondine 12.65 ----- ----- -----
H20
Ca19AI11Mg2Si18
Vesuvianite ----- 10.23 ----- -----
O69(OH)9
Mn304
Hausmannite 5.24 3.80 6.10
[MnOMn2O3]
Anatase TiO2 ----- 6.95 3.60 53.03
Rutile TiO2 9.17 ----- ----- -------
-Titanium
Ti3 05 ----- 20.32 ----- -------
oxide
Titanium
Ti203 ----- ----- 25.65 --------
oxide
Manganese
Mn2O3 ---- ----- 8.55 -------
oxide
Calcium
CaO 3.56
oxide
Fluorite Ca F2 ----- ----- ---- 14.90
Table 4. Weight percent of compounds determined from XRD.
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288 Arc Welding
Vesuvianite melt at about 1200 °C. Nefeline melts at temperatures higher than 1248 °C. The
melting of corundum, rutile, anastase, hausmannite and quartz was not detected because it
occur above 1500 °C. The zigzag behavior of DTA curves reveals blistering or gassing of the
glass formation (Gordon & Chu, 1966).
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Chemical and Physical Properties of Fluxes for SAW of Low-Carbon Steels 289
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290 Arc Welding
2.3 Effect of crystalline phases and ion contents on the behavior of flux
Oxides and carbonates were used for manufacturing the different fluxes. These formed
different crystalline phases after sintering. According to the X-ray diffraction analyses, silica
(SiO2), manganese oxide (MnO) and titanium oxide (TiO2) were the compounds that reacted
during the heating of fluxes.
The silica reacted to form anionic species such as silicates. Three compounds with this
characteristic were identified in the sintered fluxes: Nepheline (NaAlSiO4), Gismodine
(CaAl2Si2O8.4H2O) and Vesuvianite (Ca19Al11Mg2Si18O69.(OH)9). The silicon
electrodeposition in the welding cathodic pool is not as favored as the deposition of volatile
calcium from flux. It has been found (Davis & Bailey, 1991) that a small amount of silicon
can be formed electrochemically, but most of it is formed by means of calcium evaporation,
which can reduce the SiO2 in the flux.
It was found that the hausmannite (Mn3O4) was formed in the sintered fluxes. This is a
spinel with electron valences, Mn2 and Mn3. Thus, it is possible to have different reactions
which permit the formation of several oxide compounds and oxide radicals from MnO,
forming inclusions.
The ion quantification determined from the X-ray diffraction results enables us to estimate
the amount of the ions from flux formed in the plasma of electric arc. These ions react with
oxygen and the oxides will be deposited on the weld. The most important reactions between
the electric arc and welding pool correspond to those where oxygen is involved.
Oxygen can react with any cationic component from the flux, as Na1, Ca2, Mg2, Al3, Si4,
Fe2, Fe3, Mn2, Mn3, Mn4, Ti+2, Ti+3, Ti+5/3 and probably SiO4-4 from the silicates formed in
the fluxes, the anions present are O-2 and F-1.
It is possible to make a prediction of the reactions with these cations and anions. Calcium
and magnesium are expected to react first with oxygen in the welding arc because its
corresponding oxides have the largest negative formation free energy Gf. Al+3 has the next
highest value for the formation of a stable oxide. Si+4 and Titanium reacts readily with
oxygen in the next order. Ti+2 almost react at the same time with Mg+2, and then Ti+3 and
Ti+4 react to form stable dioxides to give anions and cations with similar set of reactions.
Manganese too exhibit variable valency and may form many oxides and oxide radicals
when react with the oxygen in the next order Mn+2, Mn+3 and Mn+4 in agreement with the
corresponding Gf values (Davis & Bailey, 1991).
The silicates formed will be more soluble in the slag than in the weld pool. Transfer of Mn, Si
and Al from the flux to weld pool depends on the amounts in the flux (Davis & Bailey, 1991).
The oxygen can react with any available cationic species to give non-metallic inclusions.
The identification of phases in fluxes can be used to know the behavior of fluxes during
their depositing process, as well as the effect of them on the mechanical properties of welds.
In the fluxes A, B, C, and T, the presence of corundum can be observed, which has an effect
on the facility for slag removing (Jackson, 1982). The same effect has been observed for the
presence of rutile in fluxes.
Calcium ions in fluxes increase the stability of electric arc (Butler & Jackson, 1967). These
ions can come from either oxide or fluoride compounds. Significant calcium content was
detected for fluxes A, C and T but not for flux B. Thus, the latter might present an unstable
electric arc during welding.
It is also known that quartz and corundum increase the viscosity of fluxes, while the
additions of manganese oxide, fluorite and titanium oxide reduce viscosity (Jackson, 1982).
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Chemical and Physical Properties of Fluxes for SAW of Low-Carbon Steels 291
The latter compounds were detected in the fluxes A, C, and T, but only a small content, may
be as impurity, and were observed in the flux B. Thus, a problem of flux fluidity might be
present in this flux.
The manganese oxide and quartz have been observed to have a beneficial effect on the
mechanical properties of welds (Lancaster, 1999). Manganese oxide and quartz were
included in the formulation of fluxes A and C, but not for flux B.
Titanium oxide has been observed to promote the formation of acicular ferrite, which is less
susceptible to cracking (Evans, (1996). Fluxes C and T are expected to produce the better
weld since they contain quartz, manganese oxide, titanium oxide, and the content of oxygen
ions (calculated by X-ray diffraction) is smaller than A and B.
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292 Arc Welding
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Chemical and Physical Properties of Fluxes for SAW of Low-Carbon Steels 293
Calc. Calc.
Area
Sy Suts Elongation Vickers Sy Suts
Flux Reduction Cequivalent
(MPa) (Mpa) (%) Hardness (MPa) (MPa)
(%)
A 208 410 22 47 167 0.28 446 572
B 197 418 23 51 163 0.24 407 507
C 330 551 19 36 179 0.30 565 583
T 345 569 20 43 192 0.43 586 662
Table 8. Tensile properties, hardness an equivalent carbon of welds for the different fluxes.
for most of the welds. In the case of HAZ, the ferrite mean grain size is about 5-9 m.
and T show a dendrite structure. The width of the heat affected zone (HAZ) is about 0.4 mm
Figures 9 (a)-(d) and (e)-(h) show the light and SEM micrographs, respectively, of the welds
corresponding to the fluxes A, B, C and T. Table 9 summarized the microconstituents and its
volume percentage observed in the welds corresponding to the fluxes A, B, C and T. Pearlite
and equiaxial ferrite are observed for all welds. No Widmanstätten ferrite is detected for all
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294 Arc Welding
welds. The acicular ferrite was only detected for the welds corresponding to the fluxes C
and T. This can be attributed to the TiO2 content of flux because this type of oxides favored
the nucleation of acicular ferrite at the interface between austenite matrix and inclusion
(Zhang et al. 1999) and (Babu et al. 1999). Table 9 also shows the calculated microstructure
constituents using a computer program based on the weld composition and welding
conditions (current, voltage and welding speed), (Material Algorithms Project, 1999).
According to the calculated results, no Widmanstätten ferrite is predicted to be formed for
these weld compositions, which is in agreement with the results described above. However,
the calculated results indicated no presence of Pearlite, which can be observed clearly for all
welds in Fig. 9. The calculated microstructure results also show the increase in the volume
percentage of bainite + acicular ferrite for the fluxes C and T, compared with microstructure
results for fluxes A and B. This fact shows a good agreement with the presence of acicular
ferrite observed for the welds corresponding to fluxes C and T.
The volume percentage of inclusions is show in Table 10 for the welds corresponding to
fluxes A, B, C, and T. The lowest and highest contents of inclusions are detected for the
welds of fluxes C and T, and those of fluxes A and B, respectively. Table 10 also shows the
content of oxygen ions, calculated from the flux composition. The lower the content of
oxygen ions, the lower inclusion content in the weld steel is resulted. The elongation and
area reduction percentages are shown to have a dependence on with the inclusion volume
percentage. This seems to be reasonable since the ductility is drastically decreased with the
increase of inclusions in steels (Liu & Olson, 1986).
Calculated
Acicular Calculated Calculated
Equiaxial Widmast. Pearlite Acic.
Weld Ferrite Widmanst. Ferrite (%)
Ferrite (%) Ferrite (%) (%) Ferrite+Bainite
(%) Ferrite (%)
(%)
Flux
83 0 17 0 0 1.85 98.15
A
Flux B 88 0 12 0 0 1.97 98.03
Flux
69 0 20 11 0 1.86 98.14
C
Flux T 68 0 8 24 0 1.24 98.76
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Chemical and Physical Properties of Fluxes for SAW of Low-Carbon Steels 295
Fig. 9. Light and SEM micrographs of welds for (a) and (e) flux A, (b) and (f) flux B, (c) and
(g) flux C, and (d) and (h) flux T, respectively.
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296 Arc Welding
The microanalysis on inclusions indicated that most of inclusions are aluminum and silicon
oxides, manganese and calcium sulfides; however, the presence of round and bright
titanium oxide inclusions is observed only for the welds of fluxes C and T, Fig. 10. This type
of inclusions were mainly composed of Ti, Al, Mn and Si. This fact suggests that the
acicular ferrite seems to be nucleated at the interface between austenite matrix and titanium
oxide inclusions welds. We believe that almost no TiO2 inclusions are formed for welds of
fluxes A and B because these fluxes have the lowest content of MnO. MnO was reported
(Davis & Bailey, 1991), to react with SiO2 to form silicomanganates. However, the absence of
MnO causes SiO2 to react with TiO2 to form silicotitanates. Thus, this may explain the
absence of acicular ferrite for welds corresponding to fluxes A and B. The titanium-
containing welds corresponding to fluxes C and T have the highest yield and ultimate
tensile strengths. This fact is in agreement with the formation of acicular ferrite observed for
these welds.
3. Conclusion
The determination of phase in fluxes enables us to identify the different type of oxides and
radicals formed during sintering of the initial materials. This quantification makes possible
know what anions and cations will be present in the electric arc. The most reactive reacts
quickly in the weld pool and might be either absorbed in the slag or retained in the weld as
inclusions. In summary, this work shows the importance of the selection for flux
composition in order to improve the mechanical properties of steel welds.
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Chemical and Physical Properties of Fluxes for SAW of Low-Carbon Steels 297
4. Acknowledgment
The authors wish to thank financial support from SIP-IPN-CONACYT.
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Arc Welding
Edited by Prof. Wladislav Sudnik
ISBN 978-953-307-642-3
Hard cover, 320 pages
Publisher InTech
Published online 16, December, 2011
Published in print edition December, 2011
Ever since the invention of arc technology in 1870s and its early use for welding lead during the manufacture
of lead-acid batteries, advances in arc welding throughout the twentieth and twenty-first centuries have seen
this form of processing applied to a range of industries and progress to become one of the most effective
techniques in metals and alloys joining. The objective of this book is to introduce relatively established
methodologies and techniques which have been studied, developed and applied in industries or researches.
State-of-the-art development aimed at improving technologies will be presented covering topics such as
weldability, technology, automation, modelling, and measurement. This book also seeks to provide effective
solutions to various applications for engineers and researchers who are interested in arc material processing.
This book is divided into 4 independent sections corresponding to recent advances in this field.
How to reference
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