Production Reducing

By and Kaxuo Tomoo

of Low

Phosphorous

Stainless Process*
FUNAZAKI,***

Steel

by the

Dephosphorization
KITAMURA,** TAKENOUCHI** Mitsunori

Yoshiyuki

IWANAMI***

Synopsis In order to produce stainless steel with low phosphorouscontent below 0.01 %, experimentswere carried out to find optimum conditionsfor the dephosphorizationby metallicCa and CaC2. The resultsare summarized as follows : (1) Dephosphorizationby metallic Ca should be done at temperatures below the boiling point of Ca and the composition of the steel has to be determinednot to precipitate CaC2. (2) On the other hand, dephosphorizationby CaC2 is effective high at temperatures,where the compositionof the steel has to be selectedto keep the activity of carbon in the range 0.020.3 (at 1 600 C). (3) Based upon the experiments, a new process of mixing two melts, one of which is Cr free steel dephosphorized conventional by oxidizing method and the other is Cr containing steel dephosphorized by Ca or CaC2, has been developed attain P content less than 0.01 %. to

high chromium melt dephosphorized by above mentioned reducing method. The results of the experimental and industrial tests will be described in the following. II. Experimentals The experimental apparatus is shown in Fig. 1. 250 g of mother alloy was melted in a fused Mg0 crucible (30 mmrn X 100 mm') placed in a high frequency induction furnace of 10 kVA with a graphite sleeve (37 mmIDX 50 mm01 X 150 mmrI). After holding the molten steel at selected temperatures, either Ca or CaC2 was added. Using silica tubes, about 5 g of sample were taken at the position of 5 N 10 mm above the bottom of the crucible at desired times. The atmosphere in the furnace was controlled by blowing argon gas at 1 000 cumin. As the slag got hardened by the addition of CaC2, it was stirred by tungsten rod before sampling. The phosphorous content of samples was analyzed by the molybdenum blue absorptiometric method. The purity of Ca is 99 %, and the composition of CaC2 is shown in Table 1. The chemical composition of mother alloys is shown in Table 2, where Ca was added to alloys A'-.G and CaC2 to alloys H' -.Q.

Introduction Though low phosphorous content of stainless steel below 0.01 % is known to be effective to stress corrosion cracking,l~ weld hot cracking2~ and so on, it is difficult to decrease the content by conventional oxidizing refining because of preferential oxidation of chromium. Therefore, special dephosphorization methods have been studied and these can be classified into following two methods. One is soft oxidizing dephosphorization by the slag containing Li2CO3,3~ Na2C034> or Ba05~ as principal elements which are more basic than Ca0 and have low melting point, and the other is reducing dephosphorization by CaCaF26~ and CaC2-CaF2.7~ Each of them, however, has demerits. The former needs a high flux ratio and can only achieve high degree of dephosphorization in high chromium steels below 20 % Cr. On the other hand, the latter requires high cost and leads to low productivity because of the necessity to use of ESR in the case of Ca-CaF2, and shows low efficiency of the reaction due to the errosion of refractories in the case of CaC2-CaF2. In the course of the experimental study to settle these demerits, it was made clear that reducing dephosphorization could be effectively achieved by adding metallic Ca at lower temperatures below the boiling point and sole CaC2 at higher temperatures to the molten high chromium steel. However, it was found to be difficult to reduce phosphorous content industrially below 0.01 % by these methods in case of 18 % Cr steel. Then a new process was developed to achieve low phosphorous level, where two melts were mixed. One was chromium free melt dephosphorized by conventional oxidizing method and the other was

I.

Fig.

1.

Experimental

apparatus.

Table

1.

Composition

of calcium

carbide.

(wt%)

Presented to the 99th ISIJ Meeting, April 1980, 5227 and the 105th ISIJ Meeting, April 1983, 5257, both Tokyo in Tokyo. Manuscript received September 20, 1983. 1984 ISIJ Research Laboratory, Muroran Plant, The Japan Steel Works, Ltd., Chatsumachi, Muroran 051. Melting Shop, Muroran Plant, The Japan Steel Works, Ltd.

at

The

University

of

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III.

Experimental

Results

1. Dephosphorization Ca by As Ca becomes gaseous at conventional steelmaking temperatures because of its low boiling point of 1 492 C , dephosphorization is expected to be influenced significantly by the temperature. Therefore, 1 % of Ca was added to alloy A kept at 1 36O'' 1 550 C. The change of P content with time is shown in Fig. 2. The duration time of the reaction was longer at lower temperatures and lower P content was obtained. A slight rephosphorization was observed when the melt was kept over the boiling point of Ca. Other impurities such as S, Sn, Sb, As also decrease with time, and the degree of removal of each impurity, ~J={[%i]o- [%i]t}/[%i]o X 100] at 20 min after Ca addition is shown in Fig. 3. Here, [%i]0 and [%]t are the contents of impurity i at t = 0 and t = t. It is seen from the figure that the degree of impurity removal changes suddenly at the boiling point of Ca and the change of P and Sn are especially remarkable. The effect of the amount of Ca addition on the

degree of removal of P and the other impurities at 20 min after Ca addition is shown in Fig. 4. It is seen from the figure that ~2 increases with increasing the amount of Ca addition and that more than 65 % of each impurity can be removed by the addition of Ca over 1.0 %. As mentioned above lower temperatures are favorable for the dephosphorization by Ca, so that carbon content should be raised to drop the melting point of the steel. In that case, however, suppression of dephosphorization might be expected due to the formation of CaC2. Therefore, experiments were also made at 1 420 and 1 480 C using alloys B'-G. Each value of ?P and ac at 20 min after Ca addition is shown in Table 3. Where, ac was calculated from Eq. (1). ac = f0[%C} log f c = ecc) [%CJ +e G~) {%Si]+eGC'I {%Cr] sl 91 iol = 0.19[%C]-}-0.106[%Si]-0.036[%Cr] ...........................(1)

Fig.

2.

Effect of bath temperature content with time.

on

the

change

of

Fig . 3.

Effect

of temperature

on

the

removal

of

P,

S,

Sn and Sb.
Table 2. Chemical composition of mother alloys.

%)

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Fig. Fig . 4. Effect of Ca-amount added Sb. in melt on the removal

5.

Effect content

of

flux

composition

on

the

change

of

with

time.

of P, S, As, Sn and

Table

3.

rp

obtained

by

Ca

dephos

phorization.

Fig . 6.

Effect

of bath with

temperature time.

on

the change

of P and

It can be seen from the table that remarkable increase of aC results in the suppression of dephosphorization. 2. Dephosphorization by CaC2

C content

It is known that CaC2 decomposes through contact with melt at steelmaking temperature of 1400 N 1 700 C and supplies Ca in spite of its high melting point of 2 300 C. Since produced Ca vaporizes remarkably at higher temperature over the boiling point, the control of decomposition rate of CaC2 is important to increase the efficiency of the reaction. It has been reported' that CaC2 has dephosphorization potential because of the formation of Ca3P2 by the reaction between Ca dissolved in CaF2 and P. The amount of CaF2 added to furnace or ladle, however, should be limited to prevent the errosion of linings. Therefore, the effect of CaF2 was examined as follows. The effect of CaF2 addition to CaC2 on the phosphorous change with time is shown in Fig. 5. It can be seen from this figure that though higher dephosphorization can be obtained at the beginning of the reaction by the addition of CaF2, it decreases as time goes because of rephosphorization, and that the lowest P content is obtained at the final stage of reaction in the case of without CaF2 addition. During the experiments, following phenomena such as rapid dissolution of carbon, generation of Ca flame and errosion of crucible were observed with increasing CaF2. From these facts it was considered that the efficiency of dephosphorization decreased with increasing CaF2 due to the vaporization loss of Ca at early stage and

Fig.

7.

Effect

of CaC2-amount

added

in melt

on

the degree

of dephosphorization.

the reaction with MgO which composed crucible. Accordingly, the sole addition of CaC2 was considered to be suitable for ladle treatment and the following experiments were carried out using sole CaC2. The change of P and C content with time is shown in Fig. 6 forr the experiments using alloy H and 8 % of CaC2 at 1 500'- 1 600 C. It is seen from the figure that high dephosphorization rates, corresponding to rapid decomposition of CaC2 were obtained at higher temperatures. The effect of the amount of
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CaC2 added on the degree of dephosphorization after 20 min is shown in Fig. 7. In this way the degree of dephosphorization saturates over 4 % of CaC2 addition. The change of P content with time is shown in Fig. 8 for the experiments using 45%Cr-0.54%C and 4 % of CaG2 at 1 600 C. When experiment was carried out with low initial carbon content, dephosphorization proceeded rapidly at the beginning due to the rapid decomposition of CaG2. After that, however, rephosphorization took place and the final degree of dephosphorization was decreased. Accordingly, the optimum C content is determined to be 1 2 % C for 45 % Cr steel. The change of P content with time is shown in Fig. 9 for the experiments using O'45%Cr-1 %C steel and 4 % of CaC2 at 1 600 C. It was found that the higher degree of dephosphorization was obtained with the higher Cr content. Figure 10 shows the relation between 4P(=[%P]o-[%P]t) and 4C(=[%C]t[%C]0) at the early stage of the reaction in the case of Fig. 9. As seen from the figure, 4P is directly proportional to 4C and the relation is expressed by Eq. (2). 4P = 0.0254C ........................(2) On the other hand, dephosphorization reaction is considered to be expressed by Eq. (11) as will be mentioned later, so that Eq. (3) should be given stoichiometorically. 4P = 0.864C ........................(3)

Fig . 8.

Effect

of

initial with

carbon time.

content

on

the

change

of

P content

Fig.

9.

Effect content

of

chromium time.

content

on

the

change

of

The comparison between Eq. (2) and Eq. (3) reveals that only 2.9 % of Ca produced by the decomposition of CaC2 is used for the dephosphorization. Iv. Discussion

with

1. Partial Pressureof Oxygenat ReactionInterface Recently, the effect of partial pressure of oxygen on the form of phosphorus in the Ca0-A1203 slag was studied.11~ From the results it was made clear that, when Pot was lower than about 10-18 atm, phosphide (P3-) was predominent in the melt, and that reducing dephosphorization took place. Therefore, partial pressure of oxygen in this experimentals was calculated. When metallic Ca is added to the melt kept at lower temperatures below the boiling point, the partial pressure of oxygen at the interface can be calculated by Eq. (4), where liquid Ca is supposed to be existing on the melt surface for a limited time. 2Ca0 (s) = 2Ca (1)+02 (g) 4G4) = 307100-51.28 T12)

Fig.

10.

Relation results

between in Fig. 9.

4P and 4C calculated

from the

On the other hand, when CaC2 is added to the melt kept at higher temperatures over the boiling point of Ca, Ca formed by the decomposition is considered to exist as gas phase at the interface. Therefore, the partial pressure of oxygen is calculated from Eq. (5).
2Ca0 (s) = 2Ca (g)+02 (g)
2
ca'

tog K c4~ - 4 G(4)_-log a-aP-2 log Pa = = .576T ^ ` acao 2 ...........................(4) Calculating Pot in the temperature range of 1 350 1 492 C from Eq. (4), 10-31~10-27 atm are obtained under the condition that CaC2does not precipitate.
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4G~5)= 380 200-93.24T12)

P log K(5) = --4
0

pu
2a cao 02

.(5)

.576T

= log Pot

2 log Pca+log

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The partial pressure of Ca in Eq. (5) is calculated from Eq. (6). CaC2 (s) = Ca(g)+2 C 4G~6) 61410-32.3 T 4G

log _ - 4.576T logP ca K(6) _ a2

CaC2

......(6)

logPCa+2 ac log Where, Eqs. (7) and (8) are used to calculate4G~6) CaC2 = Ca (g)+2C(s) (s) 4G)=51210-12.3T'2 C(s)=C J ............(8) 4G)=5 C8100-10.OT13) FromEqs. (5) and (6), the partial pressureof oxygen is expressed the following by equation. logP, - logK(5) logK(6) logac -2 +4

3Ca(s)+P2 = Ca3P2 (g) 4G2)=-142800+22.5T'4 1/2P2(g)=P J .. 4G3) -29 200-4.6T15) _ Ca(s)=Ca(l) 4G4) 2 070-1.85 T12) = Ca (l)+2C= CaC2 (s) 15 4G~15)-23 900+13.2T'2"3 J ...... _ ) 4G0)= -90610+37.25T...............(16) 4G1)= -18910-2.42T ...............(17) In the case of CaC2dephosphorization, equilibthe rium P content, [P]e, can be calculated from Eq. (18), which was derived from Eqs. (11) and (17), assumingthat the activity of Ca3P2 unity because is CaC2existsas solidin the slag phase.
toP ]e_ 2 _ G~11' logf ~+3 to g[ - 1 4 .576T gfc +3 log [%C] ..............................(18) Where,fp is calculated by Eq. (19), though consensus has not been obtained for ePCr) values reported up to this time. logf p = logf PC)+ fl + + f r) log log = 0.24[%C]+0.118[%Si]+ep[%Cr] ........................(19) For example, -0.037 is proposed in 11N30%Cr-P-Fe alloy by Schenck et al.,ls~ -0.025 by Frohberg et a1.17) and -0.030 by Hadrys et a1.' Therefore, ) the value ePCr> calculated from Eqs. (18) and (19) was by using the data which were thought to have sufficiently arrived at the equilibrium in Figs. 6 and 8. The obtained values for ePCr) shown in Table 4 are and are in the range of -0.040 -0.044, which is close to Schenck's value. This indicated that Cr remarkably decreasesthe activity of P in the melt. 3. Optimum Conditions Dephosphorization for Though Cr decreases the activity of P as mentioned above, high Cr content is found to be fovorable for dephosphorization. That is considered to be due to the effect of Cr which reduces the activity of C. The effectof ac on the dephosphorizationby metallic Ca at lower temperatures is shown in Fig. 12. The value of each plot is already listed in Table 3. The critical activity of carbon, ac, for the precipitation of CaC2 is calculated at 1 420 and 1 480 C by assuming aca(1) and acac2=1in Eq. (15). Cal=1 culated values of ac are 0.79 and 0.89, respectively,and
Table

=-

56 270

T --+6.28+4 ac log

......

Therefore, when CaC2 is added to the melt, Pot is calculated by Eq. (9) as functions of temperature and ac, and the relation is shown in Fig. 11. It is seen from the figure that Pot decreases remarkably with decreasing temperature and ac. As will be described later, suitable activity of initial carbon is 0.02 to 0.3 in the case of CaC2 addition and then the Pot is calculated to be lower than 10-25atm. Therefore, partial pressure of oxygen at the interface between molten steel and Ca or CaC2 is far less than 10-18atm, and from this facts reducing dephosphorization is considered to proceed. 2. Equilibrium of Dephosphorization Dephosphorization by metallic Ca at lower temperatures or by CaC2 at higher temperatures are considered to be expressed by Eq. (10) or Eq. (11) as total reaction. 3Ca (1)+2P = Ca3P2(s) ..................(10) 3CaC2+2P = Ca3P2(s)+6C ............(11) Where, standard free energy change of each reaction expressed by Eqs. (16) and (17) can be derived from Eqs. (12)N(15).

4. Calculated ePCr) from and 8.

the

data

of

Figs.

Fig. 11.

Relation between the partial pressure of oxygen, p;2 and aC in the case of CaC2 addition.

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Fig.

12.

Effect by Ca.

of ac

on

the

degree

of

dephosphorization

Fig.

14.

Effect

of aC on

the

degree

of de phosphorization

by CaC2.

Fig.

15.

A new phorous

process stainless

for steel.

the

production

of

low

phos-

Fig.

13.

Region

of e ffective

dephosphorization

by Ca.

are shown in the figure. It is seen from the figure that the degree of dephosphorization decreases in the region of CaC2 precipitation, so the composition of the steel should be adjusted to hold ac<ac. On the other hand, the melting point of the steel should be below 1 400 C, taking the temperature drop during practical operation into consideration. Accordingly, the region of effective dephosphorization by Ca is illustrated as a shadowed portion in Fe-C-Cr phase diagram'8) of Fig. 13. For dephosphorization by CaC2 at higher temperatures, aC before treatment should be adjusted low because it is increased by the pick up of carbon during the treatment. The relation between the degree of dephosphorization which is obtained from the reached values in Figs. 8 and 9 and ac before CaC2 addition is shown in Fig. 14. It is seen from the figure that high degrees of dephosphorization over 50 % can be obtained in the region of a0=0.02'-O.3. In the region of a0<0.02, however, the degree of dephosphorization decreases by the vaporization loss of Ca due to the rapid decomposition of CaC2 and it also decreases in the region of aC>0.3 due to the suppressed decomposition of CaC2.
V. Industrial From the Scale experimental Tests tests it was found that de-

phosphorization of high Cr steels can be achieved by reducing dephosphorization method. However, it is difficult to get low phosphorous content less than

0.01 % only by the reducing dephosphorizationn under unfavorable condition of industrial scale. A new process, therefore, was developed taking advantage of efficient dephosphorization in high Cr steel. The process is illustrated in Fig. 15. It is seen from the figure that high Cr steel melted in EAF(A) is decarburized to the desired carbon content and tapped into the ladle and then dephosphorized by adding Ca or CaC2 under the reducing condition with stirring. After dephosphorization, the high Cr steel melt is also decarburized to the desired carbon content by mainly VOD. On the other hand, low alloy steel melt without Cr is dephosphorized by conventional oxidizing method in EAF(B). After that both melts are mixed in the LRF (Ladle Refining Furnace), where final composition and temperature are adjusted. In the industrial scale tests, high Cr steels were melted in 25 t EAF, and Ca or CaC2 were added to the bath surface. The bath temperature just before the addition was 1 480 C for Ca and 1 575 1 680 C for CaC 2, respectively. The results of the tests are summarized in Table 5. As shown in the table, high degree of dephosphorization, 42'.'66 %, could be achieved in every run. Furthermore, heats Nos. 4, 6 and 7 using CaC2 were proceeded to the final stage of the process shown in Fig. 15, and about 90 t of 18-8 stainless steel was produced in each run. In this case, Cr free steels with high Ni content were melted in 100 t EAF, and the results are shown in Fig. 16. Though a little pick up of P occurred due to the supplemental addition of ferro-Cr during the process, low P content less than 0.01 % could be achieved.

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Table

5.

Results

of

in dustrial

scale

tests.

Table

6.

Yield

of

CaC2

for

heat

Nos.

4 to

7.

%)

Fig.

16.

Change

in P content

during

industrial

scale

tests.

Though the production of low P stainless steel has been made possible, by this process, but some problems still remain. For instance, the yield of CaC2 for heat Nos. 4~ 7 were calculated and listed in Table 6. It is found from the table that the amount of CaC2 used for dephosphorization is only about 1.5 % and, even if the amount used for desulphurization is counted, only 2.3-3.5 % of CaC2 is effectively used. Furthermore, the relation between dC and dP for heat Nos. 4~ 7 is shown in Fig. 17. As shown in the figure, the dephosphorization ratio (4Pf4C) is approximately one-half of the experimental value. Then, equilibrium P content of these heats was calculated by Eq. (18) using epCr~'-' 0.040 N -0.044. = The calculated values are in the range 0.001 -O.003 % P, which is one order of magnitude smaller than the achieved values. So that very small portion of the total calcium used effectively and that is considered to be due to the following reasons: (a) The slag off before treatment was not sufficient. (b) Calcium reacted with oxygen or nitrogen when added in the air, and others. Accordingly, methods to control the atmosphere of conditions of injection has to be studied, which is especially effective to (b). VI. Conclusions In order to decrease the P content of high Cr steel, reducing dephosphorization using metallic Ca or CaC2 were studied in laboratory experiments. Based on the experiments, a new process was developed to achieve low P content below 0.01 % P. The results are summarized as follows: (1) The optimum conditions for dephosphoriza-

Fig.

17.

Relation ment

between Nos.

JP 47.

and

4C

during

CaC2

treat-

of heat

tion by Ca are, as shown in Fig. 13, low temperature below its boiling point and ac below ac, above which CaC2 begins to form. (2) The sole addition of CaC2 is suitable for dephosphorization at higher temperatures to avoid the vaporization loss of Ca and the errosion of crucible due to CaF2 addition. High degrees of dephosphorization over 50 % is obtained by controlling the composition of melts before CaC2 treatment in the region of aC=0.02N0.3 at 1 600 C. (3) In industrial scale tests, two melts were mixed; one was chromium free melt dephosphorized below 0.002 % P by conventional oxidizing method and the other was high chromium melt dephosphorized below 0.017 % by reducing method using CaC2. As results, production of low phosphorus 18-8 stainless steel below 0.01 % P (90 t/ l heat) has been achieved.
Acknowledgements Sincere gratitude and appreciation are due to Dr.

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Saburo Kawaguchi, Plant Manager and Managing Director of Muroran Plant, The Japan Steel Works, Ltd., who permitted the authors to publish the results. The authors wish to express their thanks to Dr. Koreaki Suzuki, General Manager of Research Laboratory, Muroran Plant, for his advice and direction. Sincere appreciations are also due to Mr. Masaru Inui for his assistance to carrying out the experiments. REFERENCES 1) M. Kowaka and H. Fujikawa J. Japan Inst. Metals,34 : (1970),1047. 2) S. Kawashima,Y. Aoyama, F. Fukui, S. Inoue and K. Harada: Tetsu-to-Hagane,(1976),1386. 62 3) T. Yamauchi and S. Maruhashi Tetsu-to-Hagane, : 66 (1980),5893. 4) Y. Kawarada,K. Kaneko and N. Sano: Tetsu-to-Hagane, 68 (1982), 618. 5) T. Aokiand T. Masuo: Tetsu-to-Hagane,(1982),5292. 68 6) Y. Nakamura,N. Tokumitsu,K. Harashimaand K. Segawa: Trans. ISIJ, 16 (1976),623.

7)

H. Katayama, H. Kajioka, K. Harashima and M. Inatomi: Trans. ISIJ, 19 (1979), 635.

8) J. Chipman: JISI,180 (1955), 97. 9) H. Schenck, E. Steinmetz and P. C. Rhee: Arch. Eisenhi ttenw., 39 (1968), 803. 10) H. G. Hadrys, M. G. Frohberg and J. F. Elliot: Met. Trans., 1 (1970), 1867. 11) H. Momokawa and N. Sano : Met. Trans., 13B (1982), 643. 12) 0. Kubaschewski and E. LL. Evans : Metal Physics and Physical Metallurgy, Pergamon Press, London, (1958), 337. 13) A. Rist and J. Chipman: The Physical Chemistry of Steelmaking, John Wiley & Sons, Inc., New York, (1958), 3. 14) P. C. Ghosh and E. G. Hess: Scienceand Culture, 28 (1962), 386. 15) J. B. Bookey: JISI,172 (1952), 61. 16) H. Schenck, E. Steinmetz and H. Gitizard : Arch. Eisenhuttenw., 40 (1969), 597. 17) M. G. Frohberg, J. F. Elliott and H. G. Hadrys : Arch. Eisenhuttenw., 39 (1968), 587. 18) N. R. Grifling, W. D. Forgeng and G. W. Healy; Trans. Met. Soc. AIMS, 224 (1962), 148.

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