Transactions of the Japan Institute of Metals, Vol. 23, No.7 (1982), pp.

353 to 359

COMMEMORATIVE LECTURE

BY THE TWENTY -SEVENTH GOLD MEDALIST Of THE JAPAN INSTITUTE Of METALS

Graphitization of Weld Heat-Affected Zone in Carbon Steel*

By Minoru Okada**

It is my greatest honor to accept the 27th Gold Medal of the Japan Institute of Metals, the institute's highest award. This is attributable to the ardent collaboration of Dr. Y. Arata and my other colleagues, co-workers and students.

I started to investigate problems concerning welding and engineering at the Faculty of Engineering of Osaka University of Engineering, and Osaka University after graduating from Tohoku University in 1930. I systematized the welding engineering during my first research period, and further tried to clarify welding metallurgical problems of the heat-affected zone during the latter research period, and established the welding research system in university at the final several years there.

In this review article I will discuss the graphitization of the weld heat-affected zone in carbon steels.

1. Formation of austeno-martensite structure

Investigation of the temperature distributions, and temperature changes in the weld are the most fundamental and essential from the point view of welding engineering. The weld parts and heat-affected zone are rapidly heated and cooled by arc welding. The heating and cooling rate are very rapid. Though the formation of martensite in quenched steel is well known, the change in structure of the weld

* Commemorative Lecture, Annual Spring Meeting of the Japan Institute of Metals, Tokyo, April 2, 1982.

** Emeritus Professor of Osaka University and Honorary Member of the Japan Institute of Metals.

metal with rapid heating and cooling are still not yet clarified. We investigated the structural change in carbon steels with various cooling rates(1)(2) .

If carbon steels, in general, are heated for a short time above point A1 and then rapidly cooled, cementite in pearlite decomposes, and austenite having an extremely non-uniform carbon distribution occurs. When the austenite is quenched, martensite is formed in the main parts of the carbon-poor area and large amounts of austenite remain in the carbon-rich area. Professor Kotaro Honda called the special mixed structure of austenite and

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354

Minoru Okada

martensite "austeno-martensite" which I found in the weld heat-affected zone. The conditions of formation of austeno-martensite are as follows. Austeno-martensite appears in the main parts of the pearlite zone in the outer layer of a specimen of low carbon steel 10 mm in diameter and 50 mm in length when it is dipped for 5 to 7 s in a lead bath at 1000 to 1100°C. Though the conditions for the formation are restricted as described above, this structure is often produced in engineering practice when steels are rapidly heated and cooled in arc welding and high frequency induction heating.

A schematic explanation of the formation of the structure and the carbon distribution is shown in Fig. 1. When pearlite (1) is heated above the AC1 transformation point, lamellar cementite begins to decompose and carbon diffuses into austenite. This can be interpreted in terms of (2) to (3). The carbon distribution

Photo. 1 Austeno-martensite and ferrite in 0.2 %C steel (x 1000 x 7/9). A-M: region of austenomartensite which is in agreement with the region of pearlite before heating, F: region of ferrite which does not change upon heating.

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in steel rapidly heated and cooled is given in Figs. 1(3) and (4). Larger amounts of austenite occur in areas of higher carbon content, and the martensite appears in the main parts of areas of low carbon content. Photograph 1 shows the austeno-martensite in 0.2 %C steel. Photograph 2 represents the decomposition of cementite in 0.85 %C steel.

2. Graphitization of weld heat-affected zone in carbon steel

There have been many reports on the transformation of steel. I visited Prof. Honda in Den-enchofu, and had oppotunities to discuss the transformation of steels. I and Dr. Y. Arata have also conducted many investigations concerning the graphitization of the weld heat-affected zone in carbon steels. In January 1943, failure of a weld steam pipe took place at the Springdale station in the USA. The investigation commission reported that the failure was caused by the embrittlement of steel resulting from graphitization in the weld

Fig.2 Graphitized state in H.A.Z. of 0.7%C steel at 670°C for 260 h (x 25 x 5/6).

(a) Strucure on welding (b) Structure on reheating graphitization oeeured at region of only martensite (G)

Graphitization of Weld Heat-Affected Zone in Carbon Steel

heat-affected zone. One could, however, find few reports concerning the theoretical basis of graphitization of steel, in particular, in weld heat-affected zones. Power stations, and oil engineering plants in Japan also possess the possibility of failure in weld heat-affected zones.

We carried out the fundamental research into the graphitization of the weld heataffected zone in carbon steels(3)-(7). Figure 2 and Photo. 3 show the graphitized state in H.A.Z. of 0.7 %C steel treated at 670°C for 260 and 200 h, respectively. Graphitization occurred only in parts of the weld heat-affected zone of the steels. From careful observation of the microstructure of H.A.Z., with regard to the structure before annealing treatment, it was found that only the area which consisted of martensite graphitized upon annealing. In the area which consisted of troostite and sorbite graphitization did not occur, but cementite spheroidized. Photograph 4 represents the ready graphitization of the quenched martensite. Upon annealing at 670°C for 300 h, spheroidizing occurred in the quenched structure. Furthermore, the state of graphitization of carbon steel quenched by the Jominy End-Quenching method is interpreted in terms

Photo.3 Graphitized state in H.A.Z. ofO.7%C steel at 670°C for 200 h (x 100 x 5/6).

355

Normalized structure

Reheated structure (Spheroidized structure)

Quenched structure (Martensite)

Reheated structure (Graphitized structure)

Photo. 4(a) and (b) Normalized (a) or quenched (b), and reheated structures of Swedish commercial carbon steel (0.7%C, 0.2%Si, 0.33%Mn, 0.015%P, 0.018 %S). Size: Dia. 2 mm x length 30 mm, Preparation: Specimens were normalized or water quenched after having been kept at 1l00°C for 10 min, Treatment: Reheating at 670°C for 300 min.

of the state of the martensite of the quenched sample.

3. Carbide precipitation process on tempering of carbon steel

Carbide precipitation in quenched martensite, as mentioned above, plays an important role in the graphitization of the weld heat-affected zone. The change in thermal dilatation, magnetic properties, specific heat and electrical resistance is observed at the stage of tempering of martensite Fe-C steel. The magnetic method is effective for clarifying the tempering process because of the ferromagnetic properties of the precipitated carbides.

356

Minoru Okada

We investigated the decomposition process of martensite and residual austenite during tempering of the quenched steel using a magnetic apparatus under an alternating magnetic field, as shown in Fig. 3, which we developed ourselves(3)-(7). The apparatus is based on 'the principle of a measuring induced e.m.f. corresponding to permeability of the specimen being magnetized by the alternating magnetic field. The specimen is wound around with the non-magnetic resistance, and also wound around with a search coil and magnetizing coil (max. 100000e). Parts A and B of the secondary coil have an equal number of turns but are wound in the opposite direction. When the ferromagnetic specimen is put into side A, the balance is lost and an induced e.m.f. corresponding to the permeability of the specimen appears between end C and D.

Figure 4 shows the change in magnetization during tempering. The tempering process is divided into three stages. Jack(8) has clarified that the precipitate at the first stage is 8- carbide, using X-ray diffraction analysis. The crystal structure is a hexagonal structure with a lattice constant of a=2.752, c=4.53 A and c/a= 1.585. The chemical composition is estimated to be Fe2.1-2.4C, Hirotsu et al.(9) have reported that l1-carbide with a rhombic structure of C02N type appears in some heattreated steel of the composition. The second

stage upon tempering is the decomposition of retained austenite.

For a long period researchers using the X-ray diffraction method have discussed the carbide at the third stage of tempering of martensite with the researchers using the magnetic method. According to X-ray dif-

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Graphitization of Weld Heat-Affected Zone in Carbon Steel

fraction analysis, x-carbide at the intermediary stage between a-carbide and cementite does not appear, but only incompletely grown cementite paticlesi'".

On the other hand, we(3) and Crangle et al. (10) have claimed the presence of xcarbide using magnetic analysis(22). In particular, we nave investigated the tempering process of Swedish carbon steel with a carbon content of 0.7, 0.8 and 1.05%, and a pure iron-carbon alloy containing 1.13 %C using the above-mentioned high sensitive magnetic apparatus. Furthermore, we have electrochemically extracted the x-carbide using a double compartment electrolytic cell at hydrogen atmosphere'<"?'.

The carbides in steels have been chemically isolated(11). On the other hand, the electrolytic isolation of carbide has been utilized using electrolytes of hydrochloric and sulphuric acid since 1894(12)(13). This technique has the advantage of rapidly dissolving the specimen in the presence of less active solutions than are practicable with the chemical method. The method using solutions of HCI and H2S04 was suitable for the isolation of cementite in tempered steel, but not for the isolation of 8- and x-carbide(14)(1S). Treje and Benedicks'J'" have developed a double-compartment cell for the isolation of oxide from steel. Dr. Arata applied their method to the isolation of carbide from tempered steels, and developed the carbide-isolation method in a vacuum, and we succeeded in extracting 8- and xcarbide from tempered steels(6)(17). In Fig. 5, the anode and cathode chambers are separated by a porous diaphragm with copper serving as the cathode. The electrolytic cell is always under vacuum to prevent oxidation of the isolated carbide. Hydrogen gas is supplied from the lower part of the cell. The evacuation process is essential to prevent oxidation of the carbide because hydrogen gas is ineffective. A solution of CdBr2 ·4H20 (37.5 g in 100 cc water) is selected for the extraction of xcarbide in tempered steels. The extracted carbide is transfered to the chamber under vacuum, and then immediately kept in liquid ether. Finally the carbide is evacuated into a silica tube for long preservation.

357

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The carbide in tempered steel (® in Fig. 6(a)) and isolated carbide (® in Fig. 6(b)) exhibit the same magnetic properties as those of x-carbide (® in Fig. 6(c)) which is prepared by carburizing pure iron powder in CO gas(S)(6). The results of the X-ray diffraction analysis in Photo. 6 are in agreement with those of the magnetic analysis in Fig. 5. The structure of x-carbide is a monoclinic structure of the MnSC2 type with a= 11.562, b = 5.0595 A and {J=97.740(1B).

Recently, Ohmori et al. (20) and Imai et al. (21) using electron microscopy reported the presence of 8- and x-carbide and the transformation of x-carbide to cementite upon tempering steels. Furthermore, recent high resolution electron microscopic observation has established the transformation process of the third stage of martensite tempering'J'". .After the disappearance of s-carbide, x-carbide and cementite (O-carbide) are grown microsyntactically in the precipitated particle, and also the higher carbides On - Fe2n+ 1 C, (n ~ 3) are observed in the third stage. The x-carbide and On - Fe2n + 1 C, carbide transform gradually to O-carbide with the progress of tempering. The further investigation of the precipitation process of carbides will also be necessary.

4. Prevention of graphitization

On the transformation of the metastable higher-carbon carbide including x-carbide to cementite, the excess carbon is thought to

358

Minoru Okada

Temperature Fig. 6 Magnetic change per temperature difference of 10ce.

(a)

(b)

(c)

(d)

(e)

(f)

Photo. 5 X-ray diffraction photograph using Fe3KIX. (a) Cementite extracted from annealed 1.05 %C, (b) Cementite extracted from the steel tempered at 680cC for 5 h, (c) x-carbide extracted from the steel tempered at 400cC for 10 h, (d) Heated sample of (c) at 500cC (x-carbide+Fe304), (e) x-carbide extracted from the steel tempered at 350cC for 50 h, (f) Synthetic x-carbide.

promote the graphitization of steel. This results in the predominant graphitization in the weld heat-affected zone.

Stabilization of the carbide resulting from the preceding heating and cooling of the weld parts, or the addition of alloying elements

that possess strong affinity with carbon prevents graphitization. Though the gradient of magnetic transformation due to cementite in steels tempered below ACt is small as shown in @ in Fig. 6(a), the gradient provides the large values as shown in @ in Fig. 6(a). This implies that the excess carbon, after dissolving into austenite, entirely becomes cementite upon annealing.

We found chromium and molybdenum'V' to stabilize effectively carbides. The initiation time of graphitization is 3 h at 670°C for 0.3 %C steel annealed at 900°C for 2 h. The addition of 0.15%Cr and 0.12%Mo shifts the time to 12 hand 8 h, respectively. The addition of chromium is more effective than that of molybdenum. The alloying elements play a role in the stabilization of carbides, and of excess carbon as a nucleus of graphite to stabilize carbide. From our experimental results the addition of 1 % or more chromium is effective in preventing the graphitization of the weld heat-affected zone.

5. Conclusion

In this review article I summarized the graphitization phenomenon in the weld heataffected zone that is associated with the metallurgical fields.

For fifty years I have engaged in developing welding engineering after studying metallurgical and electrical engineering. From the view of the social needs of welding engineering researchers I planned and established the

Graphitization of Weld Heat-Affected Zone in Carbon Steel

department of Welding Engineering of Osaka University, and also laid the foundation of the Welding Research Institute at Osaka University. The department is the oldest department of welding engineering in the world. We have experienced many problems and difficulties, because the field of welding engineering is wide and belongs to former old scientific fields while the scope of other branches of engineering is already fixed. However, welding engineering and techniques have unexpectedly developed and expanded into wide fields to an extent that I could not imagine. Furthermore, I hope that welding engineering will continue to develop scientifically and technically by applying modern science and technology.

REFERENCES

(1) M. Okada: J. Iron and Steel Inst. Japan, 30 (1944), 117.

(2) M. Okada: Tech. Rep. Osaka Univ., 1 (1951), 251.

(3) M. Okada and Y. Arata: Tech. Rep. Osaka Univ., 2 (1952), 224.

(4) M. Okada and Y. Arata: Tech. Rep. Osaka Univ., 3 (1953), 311.

(5) M. Okada and Y. Arata: Tech. Rep. Osaka Univ., 5 (1955), 169.

(6) M. Okada and Y. Arata: Tech. Rep. Osaka Univ.,

359

6 (1956), 145.

(7) M. Okada and Y. Arata: J. Japan Weld. Soc. 23 (1954), 13.

(8) K. H. Jack: J. Iron and Steel Inst., 166 (1950), 17.

(9) S. Hirotsu and S. Nagakura: Acta Met., 20 (1972), 645.

(10) J. Crangle and W. Sucksmith: J. Iron and Steel Inst., 168 (1951), 14.

(11) F. Abel: Proc. Inst. of Mech, Eng., (1885), 30. (12) J. o. Arnold and A. A. Read: J. Chern. Soc., 65 (1894), 788.

(13) E. D. Campbell: J. Am. Soc., 13 (1896), 836.

(14) T. Sato, H. Kaneko and Y. Nishizawa: J. Japan Inst. Metals, 19 (1955), 336 (in Japanese).

(15) T. Sato and Y. Nishizawa: Collected Abstracts of the 1956 Spring Meeting of Japan Inst. Metals, p. 55 (in Japanese).

(16) R. Treje and C. Benedicks: J. Iron and Steel Inst., 128 (1933), 205.

(17) M. Okada and Y. Arata: J. Japan Inst. Metals, 19 (1955), 186 (in Japanese).

(18) M. J. Duggin: Trans. Met. Soc. AIME, 242 (1968), 1091.

(19) S. Nagakura, T. Suzuki and M. Kusunoki: Trans.

JIM, 22 (1981), 699.

(20) Y. Ohmori and S. Sugisawa: Trans. JIM, 12 (1971), 170.

(21) Y. Imai, T. Ogura and A. Inoue: J. Iron and Steel Inst. Japan, 59 (1973), 261.

(22) Y. Arata: Report for doctorate working in Osaka Univ., D-126, 1955.