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CALCIUM CARBIDE AS AN AGENT FOR 
 REMOVING PHOSPHOROUS AND 
 SULPHUR FROM IRON AND 
 STEEL 
 
 WILLIAM JAMES FARRELL, Jr. 
 
 THESIS 
 
 FOR THE 
 
 I) E GHEE O E B A G H E L O R O E SCIENCE 
 
 IN 
 
 CHEMISTRY 
 
 COLLEGE OF LIBEIJAL ARTS AND SCIENCES 
 
 UNIVERSITY OF ILLINOIS 
 
 1922 
 
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 ; -1 
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 v;>iv 
 
 Digitized by the Internet Archive 
 in 2015 
 
 https://archive.org/details/calciumcarbideasOOfarr 
 
UNIVERSITY OF ILLINOIS 
 
 THIS IS TO CERTIFY THAT THE THESIS PREPARED UNDER MY SUPERVISION BY 
 
 W i_l l_i ama s_ _Pa r r_e 1_1 * _ 
 
 ENTiTLED___C_aliii_.js__Caxgl.d:^__£-ii_ica_J^Sei^w_jCQj:_iic:rj3YJja^_?i2£)_ci'iiQr_ous._. 
 
 A _ ilu _f ?_QU. _ Ir_Qn_ 
 
 IS APPROVED BY ME AS FULFILLING THIS PART OF THE REQUIREMENTS FOR THE 
 DEGREE OF 
 
 
 Instructor in Charge 
 
 Approved : 
 
 ACTING HEAD OF DEPARTMENT OF .GHEMISTRY. 
 
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COFTEiTTS 
 
 Page 
 
 Acknov/ledgement 
 
 Introduction 1 
 
 Discussion 2 
 
 Laboratory V/ork 
 
 ilethods of Analysis 9 
 
 Experimental Work 
 
 Results of Analysis ..,.27 
 
 Summary of Results 
 
 General Summary 29 
 
 Coniolasions 30 
 
 Suggestion^ Eor further Work 30 
 
 Bibliography 
 
 . 31 
 
AGZIT0WLSDGSM3NT 
 
 I wish to express my sincere thanks 
 to Dr, W, S, Putnam for the keen interest 
 he has shown towards this work, and for the 
 untiring efforts and many helpful suggest- 
 ions he has made# 
 
- 1 - 
 
 INTRODUCTION 
 
 Solphur and phosphorous are the most harmful and most com- 
 mon enemies of steel. It is true that oxygen and nitrogen produce j 
 detrimental effects, hut v/ith proper treatment this objection can | 
 
 i- 
 
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 be overcome. Sulphur occurs as ferrous sulphide or as manganese \ 
 sulphide and phosphorous exists as phosphides of iron. Sulphur is 
 equally as harmful in cast iron as it is in steel, however, small | 
 amounts of phosphorous, not exceeding O.lO/a, are permissable in 
 cast iron. Up to the present time, no commercial process has 
 been devised whereby these elements have been entirely removed. 
 
 They have, however, been reduced to a point as low as 0.01 per 
 cent, but even this small amount produces detrimental effects, due 
 to segregation in certain parts of the ingot, which not only cause 
 trouble during forgiiEg in the case of steel, but also produce red 
 shortness and coarse grained structure during easting. 
 
 The patch of metal in which these segregations occur pos- 
 sesses all the properties of very inferior steel or iron, although 
 the average composition of the remainder of the metal is excell- 
 ent and an analysis of the drillings failed to reveal this trouble. 
 
 One of the best methods for detecting a sulphur segregation 
 
 is to obtain a representative polished surface and then press a 
 
 piece of photographic paper, previously soaked in hydroch2koric 
 
 acid, against this surface. If a sulphur segregation is present 
 
 fumes of hydrogen sulphide will be generated v;hich will produce a 
 brown stain upon the paper. 
 
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These segregations can also he 
 detected hy taking a microphotograph 
 of a polished surface. An analysis 
 of the drillings may fail to reveal 
 sulphur segregations, but the micro- 
 photograph will have an appearance 
 similar to that shown in the accompany- Microphotograph Showing 
 ing illustration. Sulphide Segregation. 
 
 Discussion, 
 
 The object of this thesis work is to devise a method where- 
 by the elements sulphur and phosphorous can be entirely removed 
 from steel and cast iron by use of calcium carbide as the removing 
 agent. The work on cast iron was not taken up until after several 
 tests had been made on low carbon steel, and it was found that tem- 
 peratures required to produce the desired fluidity of the molten 
 metal could not be obtained with the types of furnaces at hand. An 
 electric furnace capable of producing temperatures as high as 2000 
 degrees C, was being constructed, by lir. J. E. Eritts, but due to 
 delay in delivery of material, was not completed soon enough to be 
 used for this work. 
 
 The reactions by which the complete removal of sulphur and 
 phosphorous was expected were: 
 
 J?gS CuCg ^ CnS "|— Eo 4- 2G 
 
 Part of the calcium carbide would Jirobably be oxidized to calcium 
 oxide which would produce the following reaction: 
 

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 Si’eS -I- 2CaO -I- CaC^ it 2Fq -j- 3GaS -h 2G0 
 The phosphorous was to he removed by the reaotion: 
 
 2P^P -h SCaCg 4- 14PeO ;t fCaO^P^C^-^- 20Pe 6C0 
 
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 The chief difficulty encountered, however, is that of over- 
 coming the great affinity iron has for these two elements, namely, 
 phosphorous and sulphur* Iron combines so readily with sulphur and 
 phosphorous that it is capable of uniting with these elements, when 
 brought into contact v/ith what are considered otherwise stable com- 
 poftnds* *It has been shown tliat iron will decompose calcium sul- 
 phate according to the reaction: 
 
 CaSQ|^ -h 4Pe PeS 4- CaO 4~ 3PeO 
 
 furthermore, nearly all fuels used in the metallurgy of iron 
 and steel contain variable amounts of sulphur, which is liberated 
 as a gas and absorbed either directly or indirectly by the ferrous 
 metal. 
 
 Manganese is capable ocf taking up sulphur from iron sulphide, 
 but this compound, manganese sulphide, is soluble in both the basic 
 slag and the metal, and segregations of manganese sulphide are just 
 as detrimental to the metal as those of iron sulphide. 
 
 BecausO of the solubility of manganese sulphide in a basic 
 hlag, this compound rises to the surface where it can be oxidized 
 by the oxygen of the air with which it comes in contact, and is 
 converted into free manganese and sulphur dioxide. The sulphur 
 dioxide imsses off with the other gases, and the manganese combines 
 
 I 
 
 *The Basic Open Hearth Process — Bichmann--1911 p. 167 
 
- 4 - 
 
 with more of the sulphur oontained in the slag or metal according 
 to the following reactions: 
 
 Mn 4- FeS MnS 4- Fe 
 
 I4ciS -I- 0 2 ^ 4~ SQ 2 
 
 l&i 4- FeS ^ MnS 4- Fe, etc. 
 
 However, this reaction can never he carried to a point of less 
 than 0.01 per cent sulphur due to the reversibility of the reaction 
 as the sulphur content approaches this point. 
 
 Various other means of removing sulphur have been devised. 
 *Saniter has proposed the use of calcium chloride in conjunction 
 with a basic slag rich in calcium oxide, and made fluid by the 
 addition of calcium fluoride, but owing to the large expense in 
 both time and money this method has never been of commercial im- 
 portance. 
 
 Sulphur can be completely removed from iron only when con- 
 verted into a form which is insoluble in the metal but very soluble 
 in the slag. Galeium sulphide fulfills these conditions, but 
 according to *lProf. Osann, this compound can be produced only when 
 the slag is free from metallic oxides. Othervdse, the calcium 
 sulphide will be decomposed and metallic sulphides formed accord- 
 ing to the following reaction: 
 
 CaS 4- FeO ^ FeS -h CaO 
 
 The sulphur in the form of iron sulphide will then be 
 
 *The Basie Open Hearth Process— Diehmann— 1911 p.l70 
 *1 Stahl und Sisen — 1908 pp 873 and 1071 
 

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 immediately returned to the metal# 
 
 In order to keep the slag free from metallic oxides, reduc- • 
 ing agents such as calcium carbide must he present and for possi- [ 
 hility of the carbide free from metallic oxides very high temper- 
 atures are required# It is because of the necessity of these very 
 high temperatures that the Basic Open Hearth process fails to 
 produce steel absolutely free from sulphur segregations# 
 
 *Br. Richard Moldenke has stated that a new desulphurizing 
 agent (probably a potassium compound) had attained a wide vogue in 
 Germany# This compound, when aided to the molten metal, contained 
 in a ladle, produces a vigorous reaction, and a thin slag forms, 
 which can be skimmed off after absorption by a small amount of 
 calcium oxide. A reduction to sulphur occurred# 
 
 During recent years, experience with the production of steel 
 in electric furnaces has apparently furnished full explanation of 
 the conditions necessary for the complete removal of sulphur and 
 phosphorous from steel# 
 
 *1 Sulphur may be removed in electric furnaces by use of 
 calcium carbide, after complete deoxidation of the metal and slag 
 according to the following reactions, forming calcium sulphide, 
 Ifiiich passes into the slag; 
 
 3PeS 4- EGaO 4- CaC^ $ SFe 4- 3CaS 4- ECO 
 Very high temperatures are required for this reaction and the are 
 furnace is best adapted to produce the required temperature. 
 
 *Ghem & Met — May 10,iyES p. 887 
 
 *1 The Making, Shaping and Treating of Steel Gamp and 5’rancos 
 19E0 p. 286 
 
- 6 - 
 
 *Sulphur can iDe removed by use of silicon according to the 
 follcw^ing reactions: (l) FeS -i- Si ^ JB’e -f- SiS 
 
 (E) 2GaO -l- SiS ^ CaS ^iOg Ca 
 (3) Ga -1- 5’eS ;; OaS -i- S’e 
 
 The silicon sulphide formed partly escapes as a gas* If calcium 
 fluoride is used in place of calcium oxide for the reaction (2), 
 then the reactions, 
 
 (4) 2Ga%-l- 2SiS 2CaS + Si% -h Si 
 id) 2Ca% ■+■ ES’eS -1- Si ^ 2CaS 4- Si;^4- EITe 
 vauld occur, and the resulting calciuin hulphide would pass into 
 the deoxidized batic slag* 
 
 *1 According to S’. T. Sisco, the desire to remove phosphor- 
 ous and sulphur in electric furnace processes, often results in 
 the production of ingots full of blow holes* This he says, is due 
 to the fact that carbide slags saturated v;ith calcium sulphide lose 
 their effeciency as a deoxidizing agent, and high carbide slags 
 bdcome saturated when they contain 3*5 per cent of calcium sulphide. 
 ^Further additions of calcium carbide to the slag as desulphurizing 
 and dephosphorizing continues will result in the production of 
 metal containing only traces of these elements* However, it must 
 be remembered that deoxidation is also desired, and therefore, 
 during the deoxidizing period the slag must be kept in a reducing 
 condition v/ith only a low content of calcium sulphide. If these 
 
 *Hleetric 2’iirnaces in the Iron and Steel Industry — 
 Hodenhauser, Schoenawa, Vom Baur — 1S17 380-382 
 
 *1 Chem & Met*— Jan* 4, 1922 pp 17-23 
 
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 conditions exist then the calcium carbide will deoxidize the molten 
 metal according to the reaction: 
 
 EJ’eO-i- CaC2 Z CaO -l- 2Ce-l-2 Fe 
 
 The electric furnace is now thoroughly established and the 
 fact that no impurities are introduced during operation, along v/ith 
 the fact that very high temperatures and complete refining condit- 
 ions exist, mako it the ideal type of furnace used for the man- 
 ufacture of steel, 
 
 PHOSPHOROUS 
 
 This element, although not as objectionable as sulphur 
 should never be present in steel in amounts greater than 0,10 per 
 cent, as it tends to produce a coarse grained structure and seg- 
 regate in spots, 
 
 *As to the removal of sulphur, it requires 1,89 per cent of 
 oxygen for each per cent of phosphorous present in order th con- 
 vert it into a fom insoluble in the metal but soluble in the basic 
 slag. Oxidation can be derived only from metallic oxides and not 
 from lime as was previously supposed. Phosphorous can be convert- 
 ed into an insoluble form by the following oxidation reaction: 
 
 8P -t- 95*e0 4^ P OqUo. 5Pe 
 8 9 4 
 
 In this form phosphorous can be removed from the steel, but this 
 compound is easily attached by reducing agents and will exist only 
 in os^genous surroundings, 
 
 *1 According to Stoughton, this insoluble phosphorous com- 
 pound exists as 3Ca0,P^0 and unless the recarborizer is added to 
 
 5 
 
 *Basic Open Hearth Process- Pichmann 1911 p.l68 
 1 The Metallurgh of Iron and Steel- Stoughton P* 136 
 
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 the metal after it has bden separated from the slag the following 
 reactions will take place causing the decomposition of this phos- 
 phorous compound and the return of phosphorous to the metal: 
 2(3Ca().P205) -h 5C ^ SCaO.P^Og -h 5C0 -h 2P 
 4(3CaO.PgO^) -h 6Si S f eCaO.PgO^ ) -h bSiO^ + 4P 
 
 Therefore, in practice the recarburizer is usually added to the 
 metal, as it is pouring from the furnace* 
 
 *^eoTges Vi^ states that the relative oxidizability of phos- 
 phorous when Tjresent in molten iron is lower the higher the 
 temperature and that above 1400 degrees it is less oxidizable 
 than manganese, silicon or carbon. 
 
 *L'Age de fer, 26, 189-191 
 

- 9 - 
 
 LABORATORY V/01^ 
 
 Varioas samples of iron and steel were treated with calcium 
 carbide. Some of tliese samples before treatment with calcium car- 
 bide were treated with iron sulphide and ferrous phosphate to in- 
 crease the sulphur and phosphorous content* 
 
 The following system of marking the specimens was used, 
 li’ive tests were made and these tests were numbered from one to five, 
 The original specimen was marked with the number corresponding to 
 the test. Then the specimen which was treated to increase the 
 sulphur and phosphorous content was marked v/ith the number of the 
 corresponding test and the letter ”A” beside it. After this high 
 sulphur and phosphorous content sample had been treated with oalciui 
 carbide it was marked with the corresponding number of the test and 
 the letter "B" beside it. 
 
 *Methods of Analysis 
 
 Each sample was analized before and after each treatment to 
 determine the carbon, pjjosphorous and sulphur content. 
 
 Determination of Total Carbon 
 
 Total carbon was determined by direct combustion vi/ith oxygen. 
 The combustion train as shown in Eig. 4, was used. The sample of 
 iron or steel was placed in an alundum combustion boat, and this 
 combustion boat was placed in the center of a quartz tube, which 
 was heated to a temperature of 1,000 degrees Q by means of an 
 electric resistance furnace. The pressure exerted by the water con- 
 
 *The Bxamination of Iron, iteel and Brass — Hall and Williams 
 

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- 10 - 
 
 tained in the upper ei^t liter aspirator bottle forced the oxygen 
 out of the lower aspirator bottle and thru the combustion train* 
 Before coming into contact with the Bample the oxygen passed thru 
 a concentrated sodium hydroxide solution followed by concentrated 
 sulphuric acid* 
 
 The oxygen then passed over a coil of copper oxide and came 
 into ccntaot with the sample of steel, oxidizing any carbon pres- 
 ent to carbon dioxide* The resulting gases passed over another 
 copper oxide coil, then thru a concentrated solution of chromic 
 acid, which removed any oxides of sulphur present, and into the 
 absorption tower* Here the carbon dioxide reacted with the sodium 
 hydroxide (commercial lye), contained in this tower, forming sodium 
 carbonate and water. The water was absorbed by phosphorous pent- 
 oxide contained in the attached tube, and the excess oxygen passed 
 on thru the barium hydroxide solution, causing the precipitation 
 of barium carbonati if any carbon dioxide remained in the gas* 
 
 The absorption tower was weighed before and after absorption 
 of carbon dioxide, and the difference in weight gave the v/eight of 
 carbon dioxide formed during combustion. 5*rom this weight and by 
 knowing the weight of steel used, the percentage of carbon present 
 in the original sample was calculated. 
 
 *Jour. Ind. & 2ng ^hem. , Hov. 1921 
 
 1052 
 
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- 12 - 
 
 Determination of Sulphur 
 
 Sulphur was determined in both iron and steel by the Bamber 
 Method, ?/hich v/as chosen because it is reputed to give the most 
 accurate results, even though it requires slightly more time than \ 
 the various volumetric methods. 
 
 Procedure: Pive grams of the sample was dissolved in cone, 
 
 nitric acid, and after being completely dissolved, two grams of 
 solid potassium nitrate was added and the solution evaporated to 
 dryness on the water bath. The residue was heated to redness, and 
 after cooling, 60 cc of a one per cent sodium carbonate solution 
 was added and heated to boiling. The solution was filtered and the 
 precipitate v/ashed thoroughly with a one per cent sodium carbonate 
 soliution. The resulting filtrate was acidified with dilute hydro- 
 chloric acid and evaporated to dryness. The residue was moistened 
 with 2 cc. of cone, hydrochloric acid and 50 cc. of distilled water 
 added, and filtered. The filtrate was dilated to 100 cc. and 30 cc I 
 of a two per cent barium chloride solution added. The resulting 
 precipitate, barium sulphate, was separated by filtration, dried, 
 ignited and weighed in the usual manner. 
 
 The resulting precipitate contains 13.85/^ sulphur and by 
 
 knowing the weight of the original sample the per cent of sulphur 
 was calculated. 
 
 Determination of Phosphorous 
 Preparation of Ammonium Molybdate Solution: 
 
 Solution 1. One hundred gwams of 85^^ molybdic acid was placed 
 
I 
 
in a beaker and 240 cc of v/ater and 140 cc of aramoniuin hydrozid^ 
 solution, d. 0.90, added. The solution was filtered and 60 cc of 
 cone, nitric acid added. 
 
 Solution 2. 400 cc of cone, nitric acid and 960 cc of dis- 
 
 tilled water w'ere mixed. 
 
 When solution 1 and 2 were cooled, solution 1 was 
 added to solution 2 v/ith constant stirring. Then 0.1 gr. 
 of aimnoniuin phosphate dissolved in 10 cc of distilled water 
 was added with constant stirring and after standing for 24 
 hours the resulting solution was ready for use. 
 
 Preparation of Magnesia Mixture: 
 
 Pifty grams of anhydrous magnesium chloride were dissolved 
 in 750 cc of distilled water and then 150 cc of ammonium hydroxide, 
 d.o. 90 , was added. 
 
 Procedure: Pive grams of steel was weighed into an Krlen- 
 
 meyer flask and dissolved in 76 cc of cone, nitric acid. The re- 
 sulting solution was heated to boiling and 12 cc of strong potass- 
 ium permangate v/as added and boiling continued until manganese 
 dioxide precipitated. The manganese dioxide precipitate v;aS 
 dissolved by the addition of ammonium bisulfite solution, an ex- 
 cess being avoided. The resulting solution was boiled until clear 
 and free from brovai fumes. The solution was cooled to 35 degrees 
 C and lOOcc of ammonium molybdate solution added. After standing 
 
 for one minute the solution vms shaken for three minutes and 
 filtered. The precipitate was washed three times v/ith a two per- 
 cent nitric acid solution to free it from iron. Then it was 
 

 
- 14 - 
 
 washed I’idth a ten per cent solution of ammonium hydroxide and the 
 resulting solution allov/ed to run into a lOOoc beaker containing 
 lOcc of cone, hydrochloric acid and 0.5 gr. of citric acid. 30cc of 
 cone, ammonium hydroxide was added and then lOcc of the magnesia 
 mixture added very slowly xvith constant stirring. After two hours 
 the solution was filtered and washed v;ith a ten per cent ammonium 
 hydroxide solution* The precipitate was then placed in a porcelain 
 crucible, ignited and weighed. T^e weighed precipitate, Mg 2 P 207 , 
 contains 27.84 per cent phosphorous and from this value the per 
 cent of phosphorous in the original sample v;as calculated. 
 
, I 
 
^IXPEHIISlITAi WORK . 
 
 - 15 - 
 
 All the samples treated were melted in the oil pot furnace 
 situated in the Assay Laboratory. This furnace had an outside 
 diameter of about three feet and was about two and one half feet 
 high. The furnace v/as heated by oil forced in under a gage pres- 
 sure of about tv/enty-five pounds and mixed with a blast of air. 
 
 If was possible to maintain temperatures ranging from thirteen to 
 fifteen hundred degrees centigrade. 
 
 The molten iron or steel was poured into a sand mold made 
 by pounding moulding sand into a crucible about twelve inches high ■ 
 and five inches in diameter around an iron bar which was withdrawn 
 af^er the mold was finished. This mold was then dried in the 
 electric oven at a temperature of about 150 degrees C. for several 
 hours. An illustration of this mold is shov/n in Eig, 2. 
 
 In order to prevent oxidation the calcium carbide was added 
 in covered iron crucibles. These crucibles v;ere made of sheet iron 
 and were about two inches in diameter at the top and about two 
 inches high. The cover was fastened by means of a piece of iron 
 wire. An illustration of these crucibles is shown in ^’ig. 3. 
 
 In test No. 4 the molten iron \vas poured from the crucible 
 onto a surface of calcium carbide. The calcium carbide was 
 sprinkled over a surface of sand contained in a roasting vessel 
 constructed of a refractory material. An illustration of this 
 arrangement is shown in ^ig. 1. 
 
 Drillings for analysis were obtained by means of a shaper 
 in the University of Illinois machine shop. 
 
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- 17 - 
 
 TEST, no. 1 
 
 A ,38 carbon steel was used for this test and the original 
 was mar he d Ho. 1 and gave the follov/ing analysis: 
 
 Carbon- - 0.38 io 
 Phosphorous- - 0.082;^ 
 
 Sulphur- - 0.038/0 
 
 This piece v/as melted with the follov/ing slag in the oil pot 
 furnace. Quantity of Steel — 1,000.0 gr. 
 
 Ferrous Phosphate S»,0gr. 
 Calcium Fluoride 5.0 
 
 Aluminim Oxide 3.0 
 
 Ferrous Sulphide 28.0 
 
 ^alcium Carbonate 10.0 
 
 Silicon di-oxide 22.0 
 
 The resulting high sulphur and phosphorous content sample was 
 poured into the sand mold and later marked lA, Drillings were 
 obtained and gave the follov/ing analysis; 
 
 Carbon 0.57 io 
 
 Phosphorous 0.711 
 Sulphur 1,504 
 
 This high sulphur and phosphorous sample marked lA was placed 
 in a graphite crucible and melted v/ith the follov/ing slag. Twenty 
 grams of calcium carbide were added directly to the slag. 
 
 Steel 500.0 gr 
 
 Calcium Carbonate- 10.0 
 Calciimi Fluoride 5,0 
 
- 18 - 
 
 Alumintun Oxide 3,0gr. 
 
 Silicon Dioxide 2E.0 
 Calcium Carbide 20.0 
 
 After heating in a molten condition in the oil pot furnace 
 at a temperature of about 1500 degrees G, for one hour, the metal 
 was poured into a sand mold and allov/ed to cool slo?/ly. This 
 sample was marhed IB and drillings were obtained and analized for 
 carbon, phosphorous and sulphur. 
 
 The following analysis was obtained: 
 
 Carbon 3.19 io 
 
 Phosphorous 0.402 
 Sulphur 1.10 
 
 A comparison of the composition before and after analysis 
 follov/s : 
 
 Barb on 
 
 Phosphorous 
 
 Sulphur 
 
 Before Treatment 
 0.57 $ 
 
 0.711 
 
 1.304 
 
 Per cen$ Sulphur Removed 
 Per cent Phosphorous Removed 
 
 After Treatment 
 3.19 io 
 0.402 
 1.10 
 
 16.69f^ 
 
 43.60^ 
 
 Conclusions: This test shows that when calcium carbide is used in 
 
 large amounts there is great danger of the carbon content 
 increasing excessiTely, unless very high tempreatures are 
 used at vhiich the carbide will not decompose. However, the 
 results shov/ a decrease in the sulphur and phosphorous con- 
 tent after treatment with calcium carbide. 
 
■J 
 
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- 19 - 
 
 TSST no. 2 
 
 A sample of .38 carbon steel similar to that used in test 
 Ho. 1 was used for this test, but the temperature required to pro- 
 duce the desired fluidity of thfe metal was so high that the cruci- 
 ble being used was melted and the charge was lost. 
 
 Due to the impossibility of obtaining temperatures high 
 enough to produce a molten bath of the desired fluidity, the re- 
 maining tests were made on cast iron. 
 

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- 20 - 
 
 TEST ITO. 3 
 
 The object of this test was to determine what effect addit- 
 ions of calcium carbide and ferrous tiixide with no other slag- 
 material would produce. 
 
 A sample of cast iron, obtained at the University of Illin- 
 ois foundry, was used for this test. It was analyzed for carbon, 
 phosphorous and sulphur giving the follov/ing results: 
 
 Carbon 2,866/^ 
 
 Phosphorous 0,552 
 Sulphur 0,136 
 
 Due to the comparatively high content of sulphur and phos- 
 phorous in this original sample, no treatment to increase the 
 sulphur and phosphorous content was required. Therefore, in the 
 tabulated results of analysis samples No. 3 and No. SA are both 
 listed with the same analysis. 
 
 Sight hundred grams of this sample was placed in a crucible 
 and heated to a molten condition in the oil pot furnace. Then 
 fifteen gr.ams of ferrous oxidd and twenty- five grams of calcium 
 carbide, contained in a covered iron crucible was aiided. Heating 
 was continued and thirty minutes later the crucible was removed 
 from the furnace and the molten metal was poured into a sand mold 
 and Etliowed to cool slowly. This s£unple was marked 3B, drillings 
 obtained and an analysis made. Results of analysis: 
 
 Carbon 1 , 765 % 
 
 Phosphoroug 0.307 
 Sulphur 0.129 
 
21 - 
 
 A comparision of the analysis "before and after treatment gave 
 
 the following data: 
 Carbon 
 Phosphoroas 
 Sulphur 
 
 Before Treatment 
 
 0.552 
 
 0.136 
 
 After Treatment 
 1.765^ 
 
 0.307 
 
 0.129 
 
 5 . 14/0 
 
 44.38^ 
 
 Per cent Sulphur Removed 
 Per cent Phosphorous Removed 
 Conclusions: This test illustrates that phosphorous removal is at 
 
 a maximum and sulphur removal at a minimum when metallic 
 oxides are present. 
 
 The carbon ibontent of the iron was reduced due to reaction 
 V7ith the ferrous oxide, but the calcium carbide was probably 
 oxidized to lime, which caused the sulphur content to be reduced 
 only slightly, due to the oxidizing conditions present, promoting 
 the reaction, CaS -i- FeO ^ PeS -h CaO, 
 
-E2- 
 
 TE3T ITO. 4 
 
 The object of this test was to determine what effect 
 additions of calcimn carbide at frequent intervals would produce, 
 i’urthermore , after e^ch addition of calcium carlbide, an iddition 
 of calcimn carbonate was made with the object of producing an 
 agitation of the molten metal, due to the liberation of carbon 
 dioside, and at the same time producing a very basic slag. This 
 agitation was desired so that a more complete reaction between 
 the calcium carbide and the metal would be possible. 
 
 The sample of cast iron used in this test was obtained at 
 the University of Illinois foundry, and was marhed No, 4, Drill- 
 ings from this sample were obtained and an analysis made. 
 
 Results of Analysis: 
 
 Garb on 3,46 
 
 Phosphorous 0,440 
 Sulphur 0, 087 
 
 Then the sulphur and phosphorous content of this iron was 
 increased by treatment with the follov/ing slag material: 
 
 CO 
 
 o 
 
 phosphate 
 
 26.0 gr 
 
 Perrous 
 
 sulphide 
 
 28.0 
 
 ^alcium 
 
 fluoride 
 
 5.0 
 
 Aluminum oxide 
 
 3.0 
 
 Calcium 
 
 carbonate 
 
 5.0 
 
 Silicon 
 
 dioxide 
 
 22. 0 
 
 Quantity of cast iron treated 1300 gr. 
 
 The iron was melted with this slag material, poured into a 
 
- 23 - 
 
 mold, and allowed to cool. After cooling the sample was marked 
 llo. 4A and drillings were obtained and analyzed, 
 
 Hesults of analysis: 
 
 Carbon 2,81 io 
 
 Phosphorous 0,533 
 Sulphur 0.408 
 
 Phis sample, No. 4A, then received the following treatment. 
 1150 gr, of this iron was placed in a graphite crucible and the 
 follov/ing slag material was added, with the object of lowering the 
 sulphur and phosphorous content. 
 
 Calcium 
 
 fluoride 
 
 6.0 gr 
 
 Aluminum oxide 
 
 3,0 
 
 Calcium 
 
 carbonate 
 
 10.0 
 
 Silicon 
 
 dioxide 
 
 22.0 
 
 The crucible was then placed in the pot furnace and the 
 contents heated to a molten condition. Then a covered iron cruciblei 
 containing 35,0 grams of finely gro'ind calcium carbide v/as dropped 
 into the molten metal and the heating at a temperature of about 
 1500 degrees G, continued. Thirty minutes later another closed 
 iron crucible containg 15,0 grams of calcium carbide was added, and 
 this addition was immediately follov/ed by the addition of twenty 
 grams of calcium carbonate v/hich itvas also contained in a closed 
 iron crucible. 
 
 Thirty minutes later fifteen grams more of calcium carbide 
 was added and followed by the aftftltlon of fifteen grams of cal- 
 cium carbonate. Heating at a temperature of 1500 degrees C, was 
 continued for tv;enty minutes, and the crucible was then removed 
 

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 ■ : :'vV 
 
 
 
- 24 - 
 
 from the furnace and the molten metal poui'ed into a sand mold and 
 allowed to cool slowly. 
 
 This sample was marked Uo. 4B and an analysis made giving the 
 follov/ing results: 
 
 Car h on 3,30 io 
 
 Phosphorous 0.434 
 Sulphur 0.272 
 
 Before Treatment 
 Carbon 2.81^ 
 
 Phosphorous 0,535 
 
 Sulphur 0.408 
 
 Percent Sulphur Hemoved 
 Percent Phosphorous Kemoved 
 
 After Treatment 
 3.30 
 0.434 
 0.272 
 
 33.3 io 
 18,57% 
 
 Conclusions: This test gave a fairly efficient removal of sulphur 
 
 and phosphorous and removel appears to be more complete by 
 use of this method than by any of the previous methods tried. 
 
 The difficulty of maintainiiig the fluidity of a slag 
 so rich in lime is one objection to this type of procedure. 
 
fK . 
 
 1 
 
 
 
 1 
 
 (■ 
 
 . r?- 
 
- 85 - 
 
 TSST HO, 5 
 
 The object of this test was to determine the possibilities 
 of sulphur and phosphorous removal by first treating the cast iron 
 v/ith calcium carbide in the pot furnace, and then removing it irom 
 the furnace and pouring it over a surface covered with calcium 
 carbide. 
 
 Sample Ho 4B obtained by Test Ho, 4 waa treated during this 
 teat. The composition in regard to carbon, phosphorous and sulphur 
 was as follows : 
 
 Carbon 3,30 io 
 
 Phosphorous 0,434 
 Sulphur 0,272 
 
 This sample. Ho, 4B, was placed in a graphite crucible and 
 the following slag material added: 
 
 Calcium Pluoride 
 
 10, 
 
 ,0 
 
 gr. 
 
 Aluminum Oxide 
 
 6, 
 
 ,0 
 
 gr. 
 
 Calcium Carbonate 
 
 20. 
 
 ,0 
 
 gr. 
 
 Silicon dioxidd 
 
 30. 
 
 ,0 
 
 gr. 
 
 Calcium carbide 
 
 20. 
 
 .0 
 
 gr. 
 
 1670 grams of this iron v;as placed in a crucible and cover- 
 ed with the slag material. The crucible was placed in the pot 
 furnace and heated at a temperature of about 1400 degrees C, for 
 one hour. Then the crucible was removed from the furnace and the 
 contents poured over a sui'face of calcium carliide, an illustration 
 of which is shown in Pig, 1, 
 
 The molten metal solidified on this surface and due to rapid 
 cooling was brittle enough to be broken into piSiees, These pieces 
 

 
 
 f 
 
 « ' 
 
 ✓ 
 
 
 '.oU 
 
 '!i 
 
 f ? ' '/.Lily' J' . 
 
 I 
 
 
- 26 - 
 
 were placed in a crucible and heated to a molten state and then 
 poured into a sand mold* 
 
 After cooling the resulting sample was marked 5B, and 
 analyzed giving the follov/ing results: 
 
 Carbon 3.54 i<> 
 
 Phosphorous 0*525 
 Sulphur 0*120 
 
 Before Treatment After Treatment 
 
 Carbon 5.30 > io 
 
 Phosphorous 0*454 0*525 
 
 Sulphur 0.272 0A20 
 
 Per cent Sulphur Hemoved 55* 88^ 
 
 Per cent Phosphorous Removed 25*11^ 
 
 Conclusions: This method of treatment gives the highest removal 
 
 of sulphur and phosphorocro and seems more efficient than 
 any of the other methods studied, and it appears that the 
 sulphur and phosphorous content of the metal can be reduced 
 by allowing the metal to run over jealeium carbide as it is 
 pouring from the furnace* 
 

 
 »*• 
 
 
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 ' . > '^ « «JIM 
 
 ’f1 
 
 •■'•fTv *4E«5<' 
 
 T! 
 
 A 
 
 / 
 
33SUtTS OP 1ITALY3I3 
 
 Test No, 1 
 
 Sample No. 
 
 1 
 
 lA 
 
 IB 
 
 Garl)on 
 
 0.38 $ 
 
 0,57 $ 
 
 3.19 $ 
 
 PhospJioroas 
 
 0,082 
 
 0.711 
 
 0.402 
 
 Sulpiiur 
 
 0.038 
 
 1.504 
 
 H 
 
 . 
 
 O 
 
 Test No. 3 
 
 Sample No, 
 
 3 
 
 3A 
 
 3B 
 
 Carbon 
 
 2.866'^ 
 
 2.866"/o 
 
 1.765^ 
 
 Pho sphorous 
 
 0.552 
 
 0.552 
 
 0.307 
 
 Sulphur 
 
 0.136 
 
 0.136 
 
 U.129 
 
 Test No, 4 
 
 Sample No. 
 
 4 
 
 4A 
 
 4B 
 
 Carbon 
 
 5,45 io 
 
 2.61 1o 
 
 3.30 1o 
 
 Phosphorous 
 
 0.440 
 
 0. 533 
 
 0.454 
 
 Sulphur 
 
 0.87 
 
 0.408 
 
 0.272 
 
 Test No, 5 
 
 Sample No, 
 
 5 
 
 5A 
 
 5B 
 
 Carbon 
 
 3.50 io 
 
 3.30 ^ 
 
 5.34 °/o 
 
 Phosphorous 
 
 Q.434 
 
 0.434 
 
 0,325 
 
 Sulphur 
 
 Q.272 
 
 0.272 
 
 0.120 
 
4* 
 
 
 f 
 
 I 
 
 
 
 / 
 
 
 : 'I 
 
-S8- 
 
 
 SUMI.IARY 
 
 OP RESULTS 
 
 
 
 Original Solpliur and 
 
 Seduction in Sulphur 
 
 
 Phosphorous 
 
 Content 
 
 And Phosphorous Content 
 
 Test Ho. 1 
 
 Sulphur 
 
 Phosphorous 
 
 1.304^ 
 
 0.7ir^ 
 
 15.69 io 
 43.60 1o 
 
 Test Ho. 2 
 
 Discarded 
 
 Discarded 
 
 Test Ho. 3 
 
 Sulphur 
 
 Phosphorous 
 
 0.136/0 
 
 0.65g‘/^ 
 
 5.14 io 
 44.38 i 
 
 Test Ho. 4 
 
 Sulphur 
 
 Phosphorous 
 
 0.408^0 
 
 0.533>b 
 
 33.3 fo 
 18.57 fo 
 
 Test Ho. 5 
 
 Sulphur 
 
 Phosphorous 
 
 0.272^ 
 
 0.434^ 
 
 55.88 io 
 25.11 io 
 
1 
 
 I 
 
 i 
 
 i 
 
 + ' 
 
 T 
 
 • • 
 
 4 
 
 4 
 
 I, i*:. 
 
 •Mr«l‘--sillJ'' ^.i“- 
 
 1 ^- ‘ 
 
 » 
 
 
 r« 
 
 f;' 
 
 ) 
 
 *.v^. *■ 
 
 
 , . 'L 
 
 
-E9- 
 
 Summary : 
 
 1. V/hen sulphur removal is at a iiAxlmum then phosphorous 
 removal is at a minimum, and vice versa, due to the fact that re- 
 ducing conditions must be present during the desulphurizing period 
 and oxidizing conditions must prevail during the dephosphorizing 
 period# 
 
 2. After dephosphor ization with a slag rich in lime and 
 metallic oxides, this slag, having a high content of 3Ca(), 
 
 should be removed and a slag rich in lime and calcium carbide intro- 
 duced into the furnace during the desulphurizing period* 
 
 3. During the dephosphorizing period comparatively low 
 temperatures (l600 degrees 0, ) can be maintained, but during the 
 desulphurizing period very high temperatures (2000 degrees to 
 2500 degrees C, ) must exist so that the desired fluidity of the 
 rich lime slag will be possible and the calcium carbide ?/ill not 
 decompose# 
 
 4# Electric furnaces are the only type of furnace capable 
 of producing temperatures high enough to accomplish complete re- 
 fining of iron and steel, but because of the cost of operation are 
 somewhat prohibitive# 
 
 5, The use of an electric furnace in conjunction with a Basi: 
 Open Hearth furnace or Bessemer Converter appears to be the ideal 
 type of process for producing high grade steel# 
 

 
 I'iU JiM ^ (£: J L' 7 <';r ' ' :* “ifii 
 
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 /.Ui 
 
 
 
 
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 ♦, '-f ,. 
 
 
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- 30 - 
 
 Conclusions: 
 
 The fact that calcium carbide will exist only at very 
 high temperatures makes its use in the Basic Open Hearth furnace 
 impossible, and the application of calcium carbide to processes 
 other than electric furnace processes seems to be a process of 
 desulphurization and dephosphorization by allowing the molten metal 
 to run over calcium carbide as it lea'tes the furnace, as described 
 in Test Ho. 6. 
 
 Complete desulphurizing and dephosphorizing is not possible 
 by this method but a considerable reduction of the content of 
 these elements is effected by this method. 
 
 The danger of increasing the carbon content excessively in 
 the case of low carbon steels is present, however, high carbon 
 steel and cast iron could bo treated in this manner. 
 
 Suggestions for further V^ork: 
 
 1- The necessity of a furnace capable of producing temperatures 
 of at least 2000 degrees C cannot be too greatly emphasized in work 
 of this character. 
 
 2- With these high temperatures the importance of crucibles 
 made of refractory material capable of withstanding this heat also 
 presents itself. 
 
 3- A study of the rate of desulphurization and dephosphorizat- 
 ion with variations in time would furnish important data. 
 

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-Sl- 
 
 BIBLIOGRAPHY 
 
 B. Stoughton- - - "The Metallurgy of Iron and Steel." 
 
 1903, Published by McGraw-Hill Book Co. | 
 
 Hew York, Hew York. | 
 
 1 
 
 This book gives a good description of the manufacture and 
 mechanical treatment of steel and cast iron. It also con- 
 tains much information upon the heat treatment of steel, and 
 a discussion of alloy steels. 
 
 Hall and Williams "The Chemical and Me tallo graphic Examination of 
 
 Iron, Steel and Brass". 
 
 19E1, Published by McGraw-Hill Book Co. 
 
 Hew York, H. Y, 
 
 It is from this book that the methods of analysis used in 
 this thesis work were taken, and this book gave the most 
 complete and simple analysis method for every element in 
 steel. There are several micro-photographs shown al ong with 
 a complete discussion of me tallo graphic methods. 
 
 k. Bichmann- - - "The Basic Open Hearth Process" 
 
 1911, Published by B. VanHostrand a Co. 
 
 Hew York, H. Y, 
 
 This bock, written by a technical man gives a good des- 
 cription of the Basic Open Hearth Process and conditions required 
 for maximum .'emoval of sulphur and phosphorous. 
 
 Camp and Prancis "The Making, Shaping and Treating of Steel." 
 
 1920, Published by the Carnegie Steel Co. 
 
 , Pitt Sl->n-rp> , Pa, 
 
% 
 
 I 
 
 .L 
 
 
 O ! . 
 
 . fru - 
 
 
 
 
 » * 
 
 ^ ' •- 
 
 ‘x*'' -U'7-^ 
 
 
 
 
 
 
 
 
 
 , 
 
 
 
 
 
 ”l'' _ 
 
 . A,-* • 
 
 * ^ . ; 
 
 
 ( '. .. 
 
 ' 
 
 ’ , J.' 
 
 'V ., 
 
 
 
 
 ■ :i XV'W-) . ■ I-.' 
 
 ; .-'‘Vd 'V.- 
 
 Xl. .’ 
 
 1 • 
 
 
 
 
 .;.^^U.:^ :- 
 
 , • a. •*. 
 
 
 
 « 
 
 , ; '“/••■ ■ V • 
 
 . .. ■ ■ Ji 
 
 f 
 
 :l> 
 
 4* t 
 
 ‘:oU 
 
 " S'iv 
 
 t.. ; 
 
 • .0,. i n 
 
 iK'ii .}.'< 
 
 ■ I.'.' 
 
 
 
 > ;i ;’'„ 
 
 i 
 
 , '(7. JSift 
 
 1 j.. , I 
 
 
 { ».. 
 
 ( ■ 
 
 'M-- "Jii. 
 
 • : lo ,Xw 
 
 ' V . viv 
 
 , : c^'4- 
 
 .'■.1 ' 
 
 
 .-••itijXi 
 
 ‘ ^tL 
 
 uSV- 
 
 A... 
 
 
 .■ '» i 
 
 
 1. 
 
The complete desoription of the manafacture of all types 
 of steel as presented in this hook makes this hook in- 
 dispensihle to anyong’ interested in iron and steel. 
 
 - 28 - 
 
 C, H, ^’ulton - "Principles of Metallurgy." 
 
 1910, Published hy the McGraw-Hill Co. 
 
 Hew York, H. Y. 
 
 This is a very good hook to get the basic principles from 
 on the solution theory of carbon and iron, as well as some 
 information on metallurgical operations in general. The 
 information obtained from this book combined with a further 
 discussion as given in B. Stoughton* s "Metallurgy of Iron 
 and Steel," should make the solution theory very simple. 
 
 A, Sauveur- - "The Metallography and Heat Treatment of Iron and 
 
 Steel." 
 
 1916, Published by Sauveur and Boylston. 
 
 Cambridge, Ife,ss. 
 
 This book gives a complete discussion of steel in regard to 
 its various elements, heat treatments, and Ifetallographic 
 Methods, along v;ith numerous microphoto graphs. 
 
 Hodenhauser, Schoenawa and ^om Baur "Electric Pnrnaces in the Iron 
 
 and Steel industry. " 
 
 1917, Published by J. V/iley and Sons, Londo?'# , Eng. 
 A complete description of the manufacture of steel in elec- 
 tric furnaces is given in this book with special reference 
 to the slag material and reactions. 
 
- 33 . 
 
 PERIODICALS 
 
 Journal of the Iron and Steel Institute 
 
 This journal contains many interesting articles pertaining 
 to iron and steel among vjhich the following was most interes 
 ing and appropriate to this thesis. 
 
 J. 0, Arnold and G* B. Waterhouse- - "The Influence of Sul|ihur 
 and Manganese on Steel." 
 
 Eo. 1 1903. pp 136-160 
 
 Journal of Ind. and Engineering Chemistry 
 
 This journal although dealing chiefly with chemical re- 
 ports often contains articles an metallurgy. The article on 
 an ahsorhtion tovirer for COg was especially applicable to 
 this work. 
 
 "Sodium Hydroxide as an Absorbent for Carbon Dioxide." 
 
 Helly and Evers, h'ov. 1921 page 1052 
 
 Chemical and Metallurgical Engineering. 
 
 Several articles pertaining to this work were found in this 
 journal among which the following were most important: 
 "Deoxidation and Desulphurization in the Heroult Eurnace". 
 
 E. T. Sisco Jan. 4, 1922 pp 17-22 
 "Desulphurizing Cast Iron" 
 
 ^lay 10. 1922 p 887 
 
 Chemical Abstracts. 
 
 A summary of each of the various articles presented to the 
 
-34- 
 
 chemistry field is given in this puhlication of the American 
 Chemical Society. 
 
 The abstract of an article entitled, "The De sulphur izdt- 
 ion and Dephosphorization of Iron and Steel by Slags," 
 
 14, 2151-52 1920, was of special interest. 
 
 Journal of the American Chemical Society. 
 
 Several articles of metallurgical interest, although not 
 pertaining directly to this v/ork were found in this period- 
 ical. 
 
 The following periodicals were also consulted: 
 
 The Iron Age 
 
 The 5’oundry 
 
 The Iron Trade Heviev/. 
 

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