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Experimental Studies of the Viscosities in the CaO-FenO-SiO2 slag

Experimental Studies of the Viscosities in the CaO-FenO-SiO2 slag
Experimental Studies of the Viscosities in the CaO-FenO-SiO2 slag

Table

I.Materials Used in the Present Study

Material Purity Supplier

Calcium oxide

(CaO)anhydrous,AR grade Fisher Scienti?c (Fair Lawn,New Jersey)Iron oxide (Fe 2O 3)anhydrous,AR grade Fisher Scienti?c (Fair Lawn,New Jersey)Silicon oxide (SiO 2)proanalyze grade E.Merck

(Darmstadt,Germany)Iron (Fe)proanalyze grade E.Merck

(Darmstadt,Germany)Argon (Ar)

argon plus

AGA Gas (Stockholm)

Fig.1—Experimental setup.

Table II.

The Measured Viscosities of CaO-SiO 2and Fe n O-SiO 2Slags

Temper-ature,K Viscosity,mPa ?s CaO-SiO 2slag

(35.9pct mass CaO-64.1pct mass SiO 2)

1773176317531743173317281723171817131634.01699.51837.01999.72143.72253.32356.22459.32572.0Fe n O-SiO 2slag

(65.0pct mass Fe n O-35.0pct mass SiO 2)

175317231688167316431623157315231503

47.352.358.861.868.775.688.6112.5124.1

in the gas phase.The traces of moisture in the argon gas were removed by passing the gas through columns of silica gel and Mg(ClO 4)2,and the CO 2impurity was absorbed by ascarite kept in the gas stream.The gas was further passed through a column of copper turnings at 773K to remove the traces of oxygen.The oxygen partial pressure of the gas was monitored constantly by a ZrO 2-CaO oxygen probe and found to be about 10?9atm during both the preparation of the slags and the viscosity measurements.The slag sample was heated up to a temperature of 1753K and held at that temperature for more than 12hours.After furnace cooling,the slag was taken out and ocularly examined to ascertain that the sample had completely been melted.The slag along with the iron crucible was then stored in a desiccator before being used in the viscosity measurement.

II.

APPARATUS AND PROCEDURE

The rotating cylinder method was employed for viscosity measurements.Figure 1shows the experimental setup.A Brook?eld digital viscometer (model RVDV-3)controlled by a PC through a DV-III controller was used in the present work.The full scale torque associated with the viscometer was 7.187?10?4N ?m.The acquisition of the torque values and the calculations of the viscosities were carried out using the software supplied by Brook?eld.

A high-temperature furnace,Laboratory Furnace Group 1000,supplied by Thermal Technology Inc.(Santa Rosa,CA)was used for the measurements.The furnace had a specially designed graphite heating element and was con-trolled by a Eurotherm Model 818controller using an op-tical pyrometer sensor.The crucible containing the slag was placed in an alumina reaction tube mounted vertically in-side the furnace.Special care was taken to ensure that the crucible was positioned in the even temperature zone of the furnace.Alumina radiation shields were placed both above and below the crucible.This arrangement would ensure that the variation of the temperature in the uniform temperature zone of the furnace was less than ?3K in the entire ex-perimental temperature range.A Pt-10pct Rh/Pt thermo-couple in an alumina sheath was placed in contact with the bottom of the crucible so that the slag temperature could be measured accurately during the experiment.

The viscometer was rigidly mounted on a movable plat-form above the furnace so that it could be adjusted to be aligned to the crucible.A metal ?ange-TEFLON*bellows

*TEFLON is a trademark of E.I.Du Pont de Nemours &Co.,Inc.,Wilmington,DE.

coupling was used to close the gap between the viscometer and the alumina reaction chamber.

As mentioned earlier,the iron crucible used for the pre-melting of the slag was later employed for the viscosity measurement.The spindles used in the experiments were also made of pure iron (Armco iron)and were identical to each other.As shown in Figure 1,the spindle consisted of a bob and a shaft.The dimensions of the bob were 16mm in diameter and 27mm in height,with 45-deg tapers at the tip and near the shaft.The shaft was 4mm in diameter and 53mm in length.

In a general run,after the crucible with the premelted slag was placed in the uniform temperature zone of the furnace,the spindle mounted on the iron transducer was introduced into the alumina reaction tube.The reaction chamber was then sealed by coupling the TEFLON bellows and the metal ?ange.The length of the TEFLON bellows was adjusted to keep the iron spindle 1cm above the slag.A stream of argon gas was introduced through the gas inlet

Table III.

The measured Viscosities of Some CaO-Fe n O-SiO 2Ternary Slags Temperature,

K

CaO Pct Mass Fe n O Pct Mass Viscosities mPa ?s Temperature,

K

CaO Pct Mass Fe n O Pct Mass Viscosities mPa ?s 1753 5.5050.00155.2162324.3835.00109.31723 5.5050.00179.0157324.3835.00138.51698 5.5050.00210.7152324.3835.00183.61673 5.5050.00262.8149324.3835.00232.3175314.9535.00335.2147324.3835.00267.7172314.9535.00400.1175336.9018.00189.1167314.9535.00540.0173836.9018.00206.11753 6.9070.0022.31172336.9018.00226.51723 6.9070.0024.14169836.9018.00270.21673 6.9070.0027.88167336.9018.00325.81623 6.9070.0034.18175345.5711.00188.1175315.0050.0051.2173845.5711.00204.8172315.0050.0054.3172345.5711.00245.4172315.0050.0050.8175333.2835.0048.0167315.0050.0063.8172333.2835.0053.9167315.0050.0063.5167333.2835.0069.2162315.0050.0076.1162333.2835.0093.6162315.0050.0074.5157333.2835.00132.5157315.0050.0093.4155333.2835.00151.7152315.0050.00122.3175325.6050.0032.9147315.0050.00170.5172325.6050.0037.5142315.0050.00245.3167325.6050.0047.2172324.3835.0074.53162325.6050.0059.41673

24.38

35.00

85.9

1573

25.60

50.00

91.5

near the bottom of the furnace.The gas was led out through the gas outlet connected to the metal ?ange on the top of the furnace.After ?ushing the reaction chamber for 1hour,the ?ow rate of argon gas was reduced.Thereafter,a con-stant ?ow of argon (about 0.2L ?min ?1)was maintained during the entire course of the experiment.The slag was heated to a desired temperature at a heating rate of 5K ?min ?1.When the temperature was stabilized,the spindle,rotating at a speed of 40to 60rpm,was introduced into the molten slag by adjusting the length of the TEFLON bellows.The distance of the tip of the spindle from the crucible base was about 1.2cm,and the length of the shaft immersed in the melt was 1.0cm.The thermal equilibration time at each temperature set point was 30minutes.When the thermal equilibrium was obtained,viscosity measure-ments were carried out.Several rotation rates were em-ployed and the equilibration time for viscosity measurement at each speed of rotation was chosen to be 2minutes.The viscosity values obtained at different rotation rates were found to be in very good agreement.The viscosity meas-urements were usually carried out during the cooling cycle.However,repetitions of some measurements during the heating cycle showed very good reproducibility.

The viscometer was calibrated at 298?0.1K with four mineral oil standards with viscosities 0.0985,0.960,4.850,and 12.500Pa ?s,respectively.The viscometer was also calibrated in the temperature range of 1463to 1675K using a reference slag (consisting of Li 2O-Al 2O 3-SiO 2)developed for the BCR program of the European Union.[7]

After the viscosity measurements,some of the slags were subjected to chemical analysis using a sequential X-ray spectrometer SRS303supplied by SIEMENS*.The con-*SIEMENS is a trademark of Siemens Electrical Equipment,Toronto.

tents of CaO,FeO,and SiO 2obtained by analysis were in agreement with the weighed-in amounts within ?1pct.

III.

RESULTS

As mentioned earlier,one slag composition was chosen for both the CaO-SiO 2and Fe n O-SiO 2systems.The exper-imentally determined viscosities for the binary slags are listed in Table II.Viscosity measurements were carried out for nine CaO-Fe n O-SiO 2slags in the temperature range 1423to 1753K.The results are presented in Table III.It should be mentioned that the viscosity at each temperature listed in both Tables II and III is the average value over the experimental data obtained using ?ve different rotation rates.The maximum deviation of the experimental data from the mean values was generally found to be less than 1pct.As shown in Table III,measurements with some selected slag compositions were repeated,and the repro-ducibility of the measurements was found to be satisfactory.In all cases,the viscosity was found to decrease with the increasing temperature.

The viscosities in the CaO-Fe n O-SiO 2system at 1673K were earlier studied by different research groups.[2–5]The viscosities suggested by these researchers at this tempera-ture are compared with the present experimental data in Figure 2.While,in general,the results of the present work are within the range of the isoviscosity lines reported by Johannsen and Sishkov [4]and Kozakevitch,[5]the present viscosity values between 0.5and 1d.Pa ?s are somewhat lower than Kozakevitch’s results but agree well with the isoviscosity lines reported by Johannsen and Sishkov.The single viscosity value reported by Bodnar et al.[2]is much higher compared to the other works.Even the two values reported by Williams et al.[3]are considerably high.

Fig.2—A comparison of the present results obtained for a temperature of 1673K with the viscosities reported earlier.[2–5]

Table IV.The References of the Experimental Data Employed for the Model Calculations in the Case of Unary

and Binary Systems

System References

Unary CaO8

FeO9

SiO

210to16

Binary CaO-SiO

217to23

Fe

n O-SiO

2

20,24,and25 IV.DISCUSSION

The viscosity model developed earlier in the Division of Theoretical Metallurgy has been described in detail in an earlier publication.[1]To give an orientation to the reader, some of the salient features of the model when applied to oxide systems are presented in this section.

The viscosity,?,can be expressed by the equation

hN??G*

???exp()[1]

M R T

where h is the Planck’s constant;N is the Avogadro’s num-ber;R is the gas constant;T is the thermodynamic temper-ature;and?and M are the density and molecular weight of the melt,respectively.The term?G*in Eq.[1]is the Gibbs energy of activation for viscosity,which is consid-ered to be a function of both temperature and composition of the melt.

In the case of unary systems,the pre-exponent term in Eq.[1]can be calculated from the molecular weight and the density of the pure liquid,and the Gibbs energy of activation can be described as a temperature function in the following way:

?G*?a?bT?cT ln T? (2)

i

It has been found that the?rst two terms on the right side of Eq.[2]were suf?cient enough to describe viscosity adequately.[1]

In the case of multicomponent systems,the use of Eq.

[1]requires the molecular weight and the density of the melt.The molecular weight can be calculated by

M?X?M[3]

Σi i

where X

i

and M

i

represent,respectively,the mole fraction and the molecular weight of the component i in the solu-tion.There are a number of correlations available for de-scribing the densities in multicomponent systems.In the present model,as a?rst approximation,the average density of a solution is represented by the equation

??X??[4]

Σi i

where?

i

is the density of the pure component i in liquid state.

In the case of multicomponent systems,the Gibbs acti-vation energy can be represented as

?G*?X?G*??G*[5]

Σi i mix

where is the Gibbs energy of activation of the pure ?G*

i

component i in liquid state.The second term in Eq.[5]is due to the mutual interactions between different species and is expected to be a function of composition.In the case of ionic solutions,the Temkin description is adopted.An ox-ide ionic solution can be represented by the formula

(C1,C2,...Ci,https://www.wendangku.net/doc/ab14569199.html,)(O)[6]

P Q

where P and Q are the stoichiometric coef?cients and C1, C2,Ci,...,Cn represent different cations.The ionic frac-tion of cation Ci within the cation grouping is de?ned as

N

Ci

y?[7]

Ci

N

ΣC

In Eq.[7],N represents the number of ions,and the sum-mation covers all the cations in the system.

The term may be considered to consist of two ?G*

m ix

parts:

E

?G*????T??G*[8]

mix mix

For an ionic solution,the mixing is considered to be within each of subgroupings.Hence,when only oxygen ions are present in the anionic grouping,the term??T is expressed by only the cationic terms,viz.

???R?P y?ln y[9]

ΣCi Ci

The?E term in Eq.[8]is meant to take into account G*

mix

all nonlinear,nonsymmetrical interactions between the var-ious ionic species.This term is expressed as

E

?G*?y y y L?

ΣΣΣ

mix Ci1Ci2O Ci1,Ci2(O)

y y y y[10]

ΣΣΣΣCi1Ci2Ci3O

L?...

Ci1,Ci2,Ci3(O)

In Eq.[10],while the product in the three-power sum-

Table

V.

Optimized Model Parameters for the CaO-Fe n O-SiO 2System

Component

i Density (kg ?m ?3)Molar Weight (kg ?mole ?1)?G *i

(J ?mole ?1)CaO 3.3?103 5.6079?10?2 1.85481265?105

Fe n O 4.7?1037.1846?10?2 1.33749591?105?18.0328243?T SiO 2

2.3?103

6.0085?10?2

5.33067968?105?53.2975311?T

Binary system

?E G *m ix (J ?mole ?1

)

CaO-Fe n O ?E G *m ix (CaO-Fe n O)?y Ca y Fe (1.42179806?106

?752.941653?T )

CaO-SiO 2?E G *m ix (CaO-SiO 2)?y Ca y Si (?8.57980880?105?127.654518?T ?2.61894794?105

(y Ca ?y Si ))Fe n O-SiO 2?E G *m ix (Fe n O-SiO 2)?y Fe y Si (?9.73864634?105?266.648920?T ?2.00595129?105(y Fe ?y Si ))

Ternary system

CaO-Fe n O

?E G *m ix (CaO-Fe n O)??E G *m ix (CaO-SiO 2)??E

G *m ix (Fe n O-SiO 2)?F CFS

-SiO 2

F CFS ?y Ca y Fe y Si (?1.46016880?106?1.79190291?103?T ?4.30933880?106?y Ca

?2.16403203?106?y Fe ?4.13867392?106?y Ca 2)

Fig.3—Viscosity of Fe n O as a function of temperature.

mation represents the binary interaction of different cations

Ci1and Ci2when anion O 2?is present,the product under the four-power summation represents the three-cation in-teraction when anion O 2?is present.The binary L param-eters can be expressed as

0122

L ?L ?L (y ?y )?L (y ?y )[11]Ci1,Ci2(Aj)b b Ci1Ci2b Ci1Ci2with

k k k L ?L ?L T

[12]

b

b 1b 2where k stands for 0,1,or 2.The ternary L parameters are expressed as 01

2

2L ?L ?L y ?

L y [13]

Σ

Σ

Ci1,Ci2,Ci3(Aj)t t

m m t

m m

m ?C1,C2

m ?C1,C2

with

k k k L ?L ?L T

[14]

t

t 1t 2The choice of L parameters and how many of them

should be taken into consideration depend on the system studied.

The application of the model to the ternary system CaO-Fe n O-SiO 2requires the Gibbs activation energies for the relevant unary systems and the binary interaction param-eters.In order to evaluate these parameters,model calcu-lations were carried out for the lower order systems using the experimental information from the literature,which are listed in Table IV.The optimized parameters are presented in Table V.The density data for the three oxides are also given in the same table.The only information on the vis-cosity of liquid CaO was due to Kozakevitch,who reported that liquid CaO had a viscosity less than 0.5d.Pa ?s near its melting point.Kozakevitch’s result as a private com-munication was quoted in the Slag Atlas.[8]This value was adopted in the present calculation.The calculated results for the pure liquid FeO and SiO 2are compared with the literature data in Figures 3and 4,respectively.It is seen that the experimental data are well ?tted by the model cal-culation in both cases.In view of the importance of the CaO-SiO 2system,a number of researchers [17–23]carried out viscosity measurements for the binary CaO-SiO 2slags.These results of the researcher [17–23]were found to be in reasonable agreement.Figure 5presents the comparison be-tween the model predications and the experimental viscos-ity data by different research groups [17–23]for the CaO-SiO 2

system.It is worthwhile to mention that the present exper-imental results are in good agreement with the literature data and are well reproduced by the model calculation.Sim-ilar comparison is made for the Fe n O-SiO 2system in Figure 6.In view of the considerable disagreement between the data reported by Urbain [26]in 1951and the other groups,[20,24,25]Urbain’s values were not adopted in the pres-ent calculation.It is seen in Figure 6that the experimental results by different researchers [20,24,25]are reasonably repro-duced by the model calculation,though not as impressively as in the case of the CaO-SiO 2system.This is due to the scatters in the experimental data employed for the model calculation.Experiment in the Fe n O-SiO 2system is dif?-cult,because the oxygen partial pressure has a strong effect on the slag composition and,consequently,on the viscosity

Fig.4—Viscosity of SiO 2as a function of

temperature.

Fig.5—Comparison of the model predictions with the literature data for

the CaO-SiO 2

system.

Fig.6—Comparison of the model predictions with the literature data for the Fe n O-SiO 2system.

measurements.The experimental results reported by Ur-bain [26]are also included in Figure 6.It is seen that most of Urbain’s data are far away from the calculated values.It is interesting to point out that the present experimental data are very well ?tted by the model calculation and lie in the middle of the scatter band,as shown in Figure https://www.wendangku.net/doc/ab14569199.html,ing the experimental data for the CaO-Fe n O-SiO 2sys-tem and the parameter in Table IV,the L parameters for

this ternary could be obtained.As mentioned earlier,the isoviscosity lines in the CaO-Fe n O-SiO 2system at 1673K suggested by Kozakevitch [5]and Johannsen and Sishkov [4]were in reasonable agreement with the present experimental data.However,these values were not employed in the model calculation in view of the lack of information of the raw data.It is also worthwhile to point out that because no experimental information for the CaO-Fe n O system was available,the parameters of the Ca 2+-Fe 2+binary interaction listed in Table V were obtained along with ternary param-eters based on the present experimental results.The ?E optimized for the CaO-Fe n O-SiO 2system is also G *mix presented in Table https://www.wendangku.net/doc/ab14569199.html,ing the parameters in this table,the Gibbs activation energy for the viscosity in the CaO-Fe n O-SiO 2system can be expressed as

?G *?X ?G *?X ?G *?X ?G *?

CaO CaO Fe O Fe O SiO SiO n n 22R T (y ln y ?y ln y ?y ln y )?Ca Ca Fe Fe Si Si E E ?G *(CaO-Fe O)??G *(CaO-SiO )?mix n mix 2[15]

E

6

?G *(Fe O-SiO )?y y y (?1.46016880?10

mix n 2Fe Ca Si 36?1.79190291?10?T ?4.30933880?10?y Ca 662?2.16403203?10?y ?4.13867392?10?y )

Fe Ca The calculated isoviscosity lines at 1573,1673,and 1723K are presented in Figures 7(a)through (c),respectively.The calculated results compare very well with the experi-mental values at all three temperatures.These ?gures in-dicate that,generally,the viscosity increases as the SiO 2content increases.The increase is more profound when the SiO 2content is reaching ?0.5.

X SiO 2In Figure 8,the viscosities at different temperatures are plotted as functions of composition when the mole fraction of CaO is ?xed at 0.2.It is seen that the replacement of SiO 2by Fe n O has a strong effect on the viscosity in the high SiO 2containing slags.The viscosity decreases dra-matically as the Fe n O content is increased from X FeO ?0.25

(a

)

(b

)

(c)

Fig.7—(a)Isoviscosity line in the CaO-Fe

n

O-SiO

2

system at1573K.(b)

Isoviscosity line in the CaO-Fe

n

O-SiO

2

system at1673K.(c)Isoviscosity

line in the CaO-Fe

n

O-SiO

2

system at1723K.

to X

FeO?

0.35,irrespective of the temperature.The effect

of temperature on the viscosity is also found to be profound

in the composition range near the SiO

2

saturation boundary.

Figure9presents the viscosities at different temperatures

as functions of composition when the mole fraction of Fe

n

O

is kept constant,viz.,X

FeO?

0.5.The viscosity is found to

increase when the slag composition is approaching both the

SiO

2

and CaO saturated boundaries.

V.SUMMARY

The viscosities of CaO-Fe

n

O-SiO

2

slags have been de-

termined using the rotating cylinder technique in the tem-

perature range of1423to1753K.Iron crucibles and

spindles have been employed.The comparison of the pres-

ent experimental results with the available literature data at

1673K has shown good agreement.Calculations have been

carried out using the viscosity model earlier developed at

the Division of Theoretical Metallurgy.The model calcu-

lations have been based on the present experimental data

and the information assessed for the viscosities in the rel-

evant lower order systems.The experimental data have

been very well?tted by the model calculations in the cases

of both the CaO-Fe

n

O-SiO

2

system and the corresponding

lower systems.

ACKNOWLEDGMENTS

Partial?nancial support from the Swedish Research

Council for Engineering Sciences(TFR)for this work is

gratefully acknowledged.

Fig.8—Calculated viscosities at different temperatures,X

CaO?

0.2.

Fig.9—Calculated viscosities at different temperatures,X

FeO?

0.5.

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九年级课文翻译完整版

九年级课文翻译 Document serial number【NL89WT-NY98YT-NC8CB-NNUUT-NUT108】

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九年级英语u n i t课文 翻译 Document serial number【KK89K-LLS98YT-SS8CB-SSUT-SST108】

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