DD202894A5 - ADDITIVE FOR THE ADDITION OF VANADIUM TO IRON BASE ALLOYS - Google Patents

Abstract

The invention relates to an additive for adding vanadium to iron-based alloys. The object of the invention is to provide an additive for a vanadium additive which does not require energy for formation and which allows the effective addition of the vanadium metal constituent without the addition of carbon or nitrogen. According to the invention, the additive consists essentially of an agglomerated, blended mixture of about 50 to 70% by weight of finely divided V deep 2 O deep 3 and about 30 to 50% by weight of a finely divided calcium-bearing substance selected from a group consisting of calcium Composed of silicone alloys, calcium carbide and calcium cyanamide.

Description

239Λ80 A

Additive for adding vanadium to iron based alloys

Field of application of the invention

The present invention relates to the addition of vanadium to molten iron-base alloys, such as steel. In particular, the present invention relates to an additive composed of V ₂ O- and a calcium-containing reducing agent.

Characteristic of the known technical solutions

The addition of vanadium to the molten alloy is one of the usual requirements in the production of Sisenbasislegierungen such. Steel,

Previous industrial techniques involved the use of ferrovanadium alloys and vanadium and carbon as well as the use of vanadium, carbon and nitrogen containing materials, as disclosed in Swiss Patent Br. 4,040,814.

Although such substances are highly effective in many respects, they require processing techniques? which result in the addition of aluminum carbon and nitrogen containing materials and which therefore can not be used satisfactorily in all applications; The latter relates, for example, to the production of steel tubes and quality forged steels.

Pelleted blends of VpOe plus aluminum; V ₂ O-plus silicone plus calcium silicon alloy; V ₂ Oe plus aluminum plus calcium silicone and "red cake" plus 21 % _t 34 % or

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To date, 50 % calcium silicon alloy has been tested as a source of vanadium in steel by applying these aggregates to the surface of the molten steel. The "Eotkuchen" used is a hydrogenated sodium vanadate containing 85 % ^ ₂ ⁰ S * 9 % Ia ₂ O and 2.5% H ₃ O. The results were ambiguous, probably due to oxidation and surface degradation. Slag interference must be traced back ·

Object of the invention

It is an object of the present invention to provide a vanadium additive for iron-base alloys, and more particularly to a vanadium additive which does not require energy for formation and which, if desired, enables the effective addition of the vanadium-metal component without the addition of carbon or nitrogen.

Other objects of the present invention will become apparent from the following descriptions and claims taken in conjunction with the drawings, wherein

Fig. 1 shows the influence of the particle size on the vanadium application in the diagram and

Fig. 2 (a) to (c) represents the electron probe analyzes of steel treated according to the invention.

Explanation of the essence of the invention

The invention has for its object to provide a composition containing the vanadium in a form which is suitable to achieve the desired advantages in their addition to iron melts.

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The vanadium additive according to the invention is a mixed, agglomerated mixture consisting essentially of VpOo (at least 95% by weight of V ₀ O.,) and a calcium-containing reducing agent. The mixture contains about 55 to 65% by mass of V ₂ O ^ and 35 to 45% by mass of the calcium-containing reducing agent. In a preferred embodiment of the present invention, the reducing agent is a calcium-silicon alloy, about 28 to 32% by mass of Ca and 60 to 65% by mass of Si, primarily the phases CaSi ₂ and Si; In addition, the alloy may contain up to about 8% by weight of iron, aluminum, barium, and other impurities occasionally encountered in the manufacturing process. The manufacturing process involves the preparation of the calcium-silicon alloy by means of electro-furnace reduction of CaO and SiO ₀

with carbon. (Typical analysis values: Ca 28, 32%, Si 60 ... 65 %, Pe 5.0 % _t Al 1.25 %, Ba 1.0 %, and small amounts of impurity elements.)

In the practice of the present invention, the preparation of a blended, agglomerated mixture of VpCU and CaIcium silicon alloy is carried out in substantially the following proportions:. 50, "70 percent by weight - preferably 55 · ..65 mass percent of V ₉ Cu and 3O _e, .5O% by mass - preferably 35 · ..45% by mass - calcium-silicon alloy. The particle size of the calcium-silicon alloy predominantly (more than 90 %) has the mesh size 8 and below, ie, finer (8MxD), the V0O3 predominantly (more than 90 %) has a mesh size of 100 and finer (100MxD ).

The mixture is intimately mixed and subsequently agglomerated - for example using conventional compaction techniques - so that the VpOo particles and the

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Particles of the reductant toff it how the particles of the calcium-silicon alloy are in close contact with each other. The intimately associated agglomerated mixture is added to the molten steel, the heat of the metal bath and the reducing power of the reducing agent being sufficient to activate the reduction of the V ₂ O. The resulting metallic vanadium is immediately integrated into the molten metal.

It is important that the additive of the present invention be rapidly immersed in the molten metal so as to minimize any reaction with oxygen in the high temperature atmosphere over the molten metal, any reaction which could oxidize the caustic-carrying reducing agent. Likewise, any contact with the additive should interfere with any slag or any slag-like material on the surface of the molten metal is avoided, so that the reactivity of the additive is not affected by coating or reacting with slag. This can be achieved by several methods. For example, by dipping the additive enclosed in a container into the molten metal or by introducing the compacted mixture into the pouring stream during the transfer of the molten metal from the furnace to the ladle to ensure rapid dipping of the additive into the molten metal. if the pan should be partly, before dosing, h. be filled to a quarter or one third of the full level, and the clogging should be completed before the pan is completely filled. The CaO and SiO ₂ forming during the reduction of vanadium oxide enter the slag, unless the steel is aluminum-deoxidized. In this case, the resulting GaO modifies the results of the aluminum deoxydation practice.

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Alpo-j-Sinsohlüsse,

Because of its low oxygen content, V ₂ Oo (33 % O) is the preferred source of vanadium oxide. From this, less calcium-containing material is needed for the reduction reaction, and a smaller amount of CaO and SiO _{2 is} formed when added to the molten metal.

In addition, the melting temperature of the V ₂ O- (1970 ⁰ C) is high and thus the reduction reaction temperature

from V ₂ on plus galcium silicone alloy tight the temperature

of the molten steel (above 1500 ^° C.). The chemical and physical properties of VpOo and VpOc are listed in Table VI,

Execution Iisp

The following embodiment is also illustrative of the present invention »

Method;

In a magnesia-lined induction furnace, Armeo-iron was melted, with argon flowing through a blanket of graphite, after the temperature had been stabilized at 1600 + 10 ⁰ G, the heat was blocked with silicone. Then, - except for the vanadium addition of - setting the compositions of the amounts of heat as necessary, laughing a one-minute stabilizing the temperature at 16oo + 5 ⁰ G Hadelrohr sample for analysis was taken, thereafter, the addition of vanadium was carried out by immersing a The steel temperature was determined by the performance of the furnace for a period of three minutes after addition of V ₂ Oo plus reducing agent on one of the steel vanadium additive-containing steel foil bags into the molten steel

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Altitude of 16OO + 5 ⁰ O held. Then the heating power of the furnace was throttled; after one minute

J.- O

ben pulled and the steel poured into a 100-pound, 10.2 cm (^ dd) I ingot. Thereupon, specimens were taken from the center radius of the billet and a height of one third of the bar height from the ground and analyzed microscopically and chemically. Some of these were analyzed using an electron microprobe.

Various mixtures of ^ ₂ ^O 3 P ^ - ¹¹³ reducing agent were introduced as a Yanadium source in molten steel of various compositions. Table I gives the results in order of increasing Yanadium outputs for each of the steel compositions. The data in Table II compares the Yanadium Exposures for different grades of steel in those cases where the yanadium additions were at different pressures kqmpakti _: mixtures of YpOo plus '': GaIcium-silicon alloy (8MxD); for the data in Table For the sake of more complete characterization of the preferred mixture of Y'0-, plus calcium-silicon alloy, the particle size distribution of the technically predetermined 'alpha-silicon alloy (8MxD) is shown in Table IY. It should be noted that 67 % is less than 12 mesh and 45 % less than 20 mesh As shown in Figure 1, the finer particle size fractions of the calcium-silicon alloy are effective in reducing the Vp ^ 3, yet the 8MxD approach is not only a less expensive, but also a less hazardous, product than the finer ones Fractions.

For some types of steel, the addition of carbon or carbon and nitrogen is either possible or even useful.

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borrowed. As shown in Table Y, by reducing the YpO, with CaC ₂ or CaCl ₂ , vanadium can be added to these steels as well as carbon or carbon plus nitrogen.

As mentioned above, the Table I the experimental heat values in order of increasing vanadium recovery for each steel composition represents · It should be noted, dai3 reducing substances such as aluminum and aluminum with Terschiedenen flow agents Vq®3 ^ ⁿ S ^esciimo l ^2e ~ nem steel · For all these mixtures,

However, the vanadium emissions in the steels less than 30 % o

As can be seen from Table I and Figure 1, the optimum vanadium outputs were determined when the Vanadiua source was a tightly coupled mixture of 60 % VpOo (100MxD) plus 40 % CaIcium-Silicone alloy (8MsJD). It is further noted in Table I that the vanadium spreads are independent of the steel compositions. This is particularly evident in Table II where the vanadium output is made from the mixtures of 60% VpO, plus 40 % Galcium-Silicone Alloy. 8MsD, for aluminum killed steels (0.08 .., 0.22% C), for semi-killed steels (0.18 ... 0.30 f <ß) and for unalloyed carbon steels (0.10 ».. 0.40 % C) exceeded 80 % . In addition, Table II shows that vanadium coverage progressively improved as the 60 % V ₂ Oo plus 40 % calcium-silicon alloy (8MxD) blend, rather than being manually packed into the steel foil immersion pouches by a technical compaction process In other words: the close connection of the mixture of V ₂ O ^ plus CaIcium-silicon alloy, such as by the large-scale briquetting with

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is characterized by a binder j, improves the vanadium deliveries The heat values in the case of the addition process highlighted in Table II by square border, for example, were designed as a double heating with the exception of the preparation of the addition mixture. For almost all heat pairs, the vanadium emissions from the engineered briquettes exceeded those of the manually packed mixture of steel foil bags.

The data in Table III illustrate the "effect of the particle size of the reducing agent, the calcium-Sriikon"

Alloy, on the optimization of vanadium emissions. Again, the vanadium outputs were independent of the steel compositions and reached their maximum values when the particle size of the calcium-silicon alloy was 8MxD or below, as shown in the graph of Figure 1. Although high vanadium outputs of over 90 % were measured when the particle size ranges of the GaIcium-Silicone alloy were 150MxD and 100MsD, the potential hazards and costs associated with production of these magnitudes limits their industrial application. For this reason, the 8MsD calcium-silicone alloy with its properties is optimally suitable for use in the context of the present invention. The particle size distribution of 8MsD technical grade is given in Table IV.

Are slight increases in the carbon or carbon-plus-nitrogen contents in the steel manufacturers is acceptable or even you advantage, then, instead of the calcium-silicon alloy CACP and / or CaCl ₂ ^a ^ ^s may be a reducing agent, are used. It has been shown that also technical CaC and CaCHP are effective for reducing VgOo

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and not only to add vanadium, but also to add carbon or carbon and nitrogen to molten steel. The results listed in Table V indicate the vanadium emissions and the increases in carbon and nitrogen contents of molten steel after adding VgOo plus CaC ₂ and VgO ₂ plua CaCTp mixtures.

Test pieces removed from the bars were chemically analyzed and visually inspected. Often the insets in the polished sections were analyzed by electron microscopy. During this investigation, it was found that the CaO produced by the reduction reaction modified the characteristics of the alumina inclusions of aluminized oxide steels. This can be seen, for example, in the electron-satellite representations of Figure 2 _3, where calcium and aluminum occur side by side in the inclusions. Thus, addition of VjO, plus calcium-containing reducing agent to molten steel according to the present invention is not only a vanadium source, but the resulting calcium oxide also modifies the adverse effects of alumina inclusions in aluminum-deoxidized steels. The degree of modification depends on the relative amounts of CaO and AlpO- in the molten steel.

It will be seen from the foregoing that a closely linked agglomerated mixture of V "0o and a carbonaceous reducing agent is an effective and energy source of vanadium when immersed in molten steel.

The screen sizes referred to herein refer to the U, S screen nomenclature.

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Table I

Yanadiusnzusätze to steel

l · 7r. steel type

Heat V source

'3 ' reducing substance ^d) identity masa

1 low carbon: J635 65 0.036 to 0.05 % Al 0.10 to 0.12 % C 0.16 to 0.31 % Si 1.50 to 1.60% Mn

2 J636 67

3 J639 65

4 J637 65

5 J647 60

6 J645 60

7 J676 60

8 J644 60

9 J641 60

10 J619 65

11 J615 50

12 J614 55

13 J620 60

14 J798 60

15 J800 60

16 J799 60

17 carbon steels: J654 60 0.03 to 0.07 % Al 0.23 to 0.29 % C 0.27 to 0.33 % Si 1.35 to 1.60 % Mn

18 J672 65

19 J671 55

20 J669 65

21 J670 70

22 J657 60

23 J656 60

24 J655 60

Al 32

+ 3 % 40 % Cryolite Pließm. + 60 % GaP ₀ (oil)

CaP ₀ (Pließm.) 3 Al ² 30 al 35 al 35 "Hypercal" 40 CaSi 40 CaSi 40 CaSi 40 CaSi 40 CaSi 35 CaSi 50 CaSi 45 CaSi 40 CaSi 40 CaSi 40 CaSi 40 CaSi 40

CaC ₂ CaC ₂ CaSi CaSi CaC ₂ CaSi CaSi

35 45 35 30 40 40 40

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Table I (continued)

Mr. ₉ Particle size Y addition ~ o s proceed ^} % added vanadium % 1 out of % C kiln "3 niin" 1 powder P 0.25. 4 2 Powder - P 0.25 • 10 3 7-100M (granules) P 0.25 36 4 shot P 0.25 52 5 1/8 " P 0.25 64 6 1/4 " P 0.25 72 7 1/2 » P 0.25 76 8th 1/8 " P 0.25 80 9 1/8 » P 0.25 80 10 8MxD P 0.13 80 11 3MsD P 0.13 85 12 BMSD P 0.13 87 13 8MxD P 0.13 88 14 150MxD B 0.25 92 15 8MxD BO 0.25 92 16 100MxD B 0.25 '96 17 1/8 " P " 0.20 75 18 1/4 "X1 / 12" P 0.20 76 19 1/4 ^H x1 / 12 » P 0.20 77 20 8MxD P 0.20 79 21 8MxD P 0.20 81 22 1/12 "x1 / 4 ⁿ P 0.20 83 23 8MxD P 0.20 87 24 8MxD P 0.20 90

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Table I

yanadium additives to steel (porting)

ur, steel type or /O Cf /O Si Mn Heat- V- Ir. % Source ¹ T ₂ O ₃ ^/ Reducing ^Agent Identity Mass Percent 40 35 45 50 2t) 26 27 28 Jb78 3 ^ J677 ^zs J679 ** J680 ^xs No. 65 55 50 GaGU ₂ CaCl ₂ CaCI ₂ CaCl ₂ 35 29 J674 65 CaSi 40 30 Carbon steels: 0.04 to 0.07 % Al 0.15 to 0.20 % C 0.22 to 0.28 % Si 1.40 to 1.50 Å J675 60 CaC ₂ 35 31 J676 65 CaC ₂ 40 32 Unalloyed carbon steel 0.19 to 0.29 % 0.54 to 0.85 % - · Si Mn J673 60 CaSi 40 40 40 33 34 35 J634 J699 J673 60 60 60 CaSi CaSi CaSi 40 36 J7T4 60 CaSi 40 37 J734 60 CaSi 40 38 J747 - 60 CaSi 40 40 40 39 40 41 J709 J708 J707 O O O VO VD VD CaSi CaSi CaSi 40 42 J702 60 CaSi 40 43 J735 60 CaSi 40 44 J700 60 CaSi 40 45 J701 60 CaSi, .. 40 40 40 46 47 48 J710 J711 J713 60 60 60 CaSi CaSi. qasi 40 49 Carbon steels: 0.03 to 0.07 % Al 0.27 to 0.33 % Si 1.35 to 1.60 % Mn J7O6 60 CaSi 40 50 J7O5 60 CaSi 40 51 J7O3 60 CaSi 40 52 J712 60 CaSi 40 53 Permanently stabilized: 0.07 to 0.12 0.62 to 0.71 J704 60 CaSi

Footnotes see next page '(d. U ₄

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Table I (port setting)

Ήτ, Particle V addition % added % Y % C

Size method ^J Vanadium introduced Qf en- "3 min"

P 0.20 50

P 0,20 55

P 0,20 60

P 0,20 60

B 0.20 80

P 0.20 85

P 0.20 85

B 0.20 85

P 0.25 68 * 0.08

loose 0.20 81 0.17

B 0.20 85 0.13

P 0.20 86 0.16

BG 0.19 39 0.08

.BC 0.21 90 0.10

P 0.149 75 0.30

P 0 _s 15 75 0.21

P 0.16 79 0.1.6

BC 0.15 89 0.38

3C 0,20 90 0,08

BO 0.16 93 0.10

BG 0.16 93 0.25

P 0.15 75 0.10

P 0.17 85 0.20

BG 0.17 86 0.38

BC 0.15 88 0.40

BG 0.15 88 0.31

BG 0.15 90 0.11

P 0.18 92 0.29

BG 0.16 92 0.18

25 325M 26 325M 27 325M 28 3 251 29 8MxD 30 16IÄxD 31 16MxD 32 8MxD 33 8MxD 34 8MxD 35 8MxD 36 8MzD 37 8MxD 38 8MxD 39 8MxD 40 8MxD 41 8MxD 42 8MxD 43 70MxD 44 8BIxD 45 8KxD 46 8MxD 4.7 8MxD 48 8MxD 49 8MxD 50 8MxD 51 8MxD 52 8MxD 53 8MxD

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Footnotes to Table II

' Probably, faulty result

^IJ vanadium source: T ₂ O ₃ - over 99% pure, 100MsD (commercial product UGG),

' Reducing agents: GaSi alloy - 29 »5% Ga, 62.5 % Si, 4.5 % Pe, trace amounts of Mn, Ba, Al, G, etc.

(Commercial product UCG).

CaCH ₂ over 99% purity, 325MxB (chemical reagent),

CaC ₂ - foundry grade, 56.5 % CaC ₂ (commercial product,

UGC) - (i / 4 "rt / 12 ^w particle size).

Al powder Alcoa quality no. 12-1978.

»Hypercal» - 10.5 % Ga, 39 % Si, 10.3 % Ba, 20 % Al, 18 % Pe.

Bi. Briquetted in a hand press; no binder

P: densely packed in steel foil pouches. Loose: Introduced in dipping capsules, - not packed. BG: Briquetted in industrial process - with binder,

All the above additions were made by thawing. The Yanadium Supplemental Mixtures are added to the molten steel after insertion into low-carbon steel foil bags.

eue *) J Approximately 10 pounds of the metal were released from the furnace when the V ₂ Oo + CaCH _{2 was} immersed.

λ Q ηΠ HQAQ * 0 ^ hS

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Table II

Influence of packing density and steel compositions on the vanadium discharges Vanadium source: 60 % V ₃ O ₃ + 40 % CaSi (8MxD)

Hr, heat % Y ' addition,

Ur, added procedure ''

Composition of the furnace "3 min" Hadelrohres (steel)

J620 0.25 P % C % Si % A 1 1 ^: J673 0.13 P 0.077 0.24 0.057 2 J714 0.20 B 0.085 0.30 0.059 3 J699 0.20 P 0.130 0.23 0.074 4 J655 0.20 no P 0.16 0,275 0,061 VJL J656 0.20 P 0.17 0,284 Ö, O63 6 J734 · 0.20 P 0.21 0.29 0,055 7 J747 0,186 BC 0.22 0.32 0.05 8th J700 .2052 BC 0.08 0.16 no Al 9 J707 J701 0.172 BC 0.10 0.39 added 10 J708 0.20 0.172 P 0.18 0,069 11 J702 0.20 0.16 0.25 0.107 0.069 J7O9 0.172 BC 0.21 0.106 12 J7O3 0.20 ρ 0.38 0.097 13 J710 0.172 BC 0.30 0.121 14 J704 0.20 P 0.11 0.21 15 J711 J7O5 0.172 BC 0.10 O, 245 ~ 16 J712 0.20 0.172 P 0.18 0.195 / 17 J7O6 0.20 BC 0.20 0.31 0.287 0.233 core Al 18 J713 0.172 P 0.29 0.253 added 19 0.20 0.40 0.224 20 BC 0.38 0.252 21 P 22 BC 23 P >

The vanadium additions were made by placing steel foil bags in the molten steel (166O ⁰ C + 5 ⁰ C), the bags containing the mixtures of the 60 % V _? 0 ₃ + % 0% contained CaIcium silicone alloy. The mixtures were placed in the pouches as follows: 1) densely packed mixture (P); 2) not packed (no P); 3) briquetted in a hand press - no binder (B) or 4) briquetted in an industrial process - with binder (BC),

Probably faulty result

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table II (3 ? Ortsetsung) % Y ' Spreading < mild · f Mr. % Mn % 1 68. - S Carbon steel 1 1.49 0.16 88 Al-killed 2 1.51 0.114 85 increasing increasing 3 1.51 0.17 86 E-content C-content 4 1,514 0.172 81 5 1,609 O, 161 90 β 1.64 0,180 87 χ 7 1.69 0.17 89 - 8th 0.50 0,165 93 Half 9 0.82 0.19 93 calmed down 10 0.657 0.16 79 increasing 11 0.704 0.158 93 G content 12 0.64 0.16 75 13 0.704 0.15 89 14 0.708 0.153 75 15 0.626 0.543 0.149 0.154 0.573 0.15 90 16 0.543 0,159 75 11 Ο, 616 0.873 0.17 0.152 92 18 0.861 0.183 85 19 0.831 0,152 0.845 0.172 88 20 92 21 88 22 86 23

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Table III Influence of particle size of calcium

Silucon alloy on the Yanadium application from Yanadiumoside in steel

Mr. Heat Y source GaSi

Mr. % Y ₃ O ₃ %

~ "i Carbon 0.036 to 0.05 % Al

_o substance 0.10 to 0.12 % G

* poor: 0.16 to 0.31 % Si 3 1.50 to 1.60% Mn

9 carbons 0.04 to 0.07 % Al

, _n- matter 0.23 to 0.29 % G

^ιυ stestahl 0.27 to 0.33 % Si

11 1.35 to 1.60% In J655

12 half 0.19-0.40% Si _Λ ~. from 0.60 to 0.80% Mn ¹ h: 0.08 to 0.10 % C

J798 60 40 J799 60 40 JBOO 60 40 J645 60 40 J646 60 40 J644 60 40 J641 60 40 J640 60 40 J654 60 40 J656. 60 40 J655 60 40 J735 60 40 J747 60 40

² T: tightly packed in steel foil pouches.

B: Briquettes made in a hand press and packed in steel foil bags.

BG: Briquettes made in a briquette industry and packed in steel foil bags.

In the three methods mentioned here, the addition was carried out by placing the bags in molten. Steel at 16ΟΟ + 5 ⁰ C.

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table III (port reduction; % V % 1 Ir .. particle Dosage added Spreading size retracts, 0.25 92 1 150MxD B 0.25 96 2 100IxD B 0.25 92 3 8MxD σ 0.25 72 4 1/4 » ρ 0.25 76 VJL 1/2 " P 0.25 80 6 1/8 » P 0.25 80 7 1/8 " P 0.13 88 8th 8MxD P 0.20 75 9 1/8 " P 0.20 87 10 8MxD P 0.20 90 11 8MxD P 0.195 90 12 70MxD BC 0,205 93 13 70MxD BG

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Table IV Particle size distribution of calcium

Silicone Alloy (8 Mesh x Down)

6 tabs - maximum

4 % to 8 m

33% to 12 1

55 56 to 20 m

68 % to 32 m

.78% on 48 m

85 % to 65 m

89% to 100 m

93% to 150 m

95 % to 200 m

Products of Union Carbide Corporation, Metal Division

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Table V

Vanadium additives for carbon or carbon plus nitrogen containing steel

Warmth-

Reducing agent ²

C.J

Id enfrity

particle

size

Carbon steel: 0.03 to 0.7 % Al 0.23 to 0.29 % C 0.27 to 0.33 % Si 1.35 to 1.60 % Mn

Carbon Toffs: 0.04 to 0.07 % Al 0.15 to 0.20 % C 0.22 to 0.28 % Si 1.40 to 1.50% Mn

J672 J671 J657

J678 ^X J677 ^X

J675 J676

65 55 60

60 65 55 50 60 65

CaC,

CaC,

35 1/4 "s1 / 2»

CaCl _{2 2} 40

CaCU ₂ 35

CaClT ₂ 45

CaOT ₂ 50

CaC ₂ 40

CaC ₀ 35

200M 200M 200M 200M 16MxD 16MxD

CaC

CACIT

: over 99 % purity, 100MxD (commercial product, UCC).

: 80 % CaC ₀ , 14 % CaO, 2.9 % SiO ₀ , 1.6 % Al ₀ Oo (commercial product UCC). ^{ά ά} *

₂ :

50% Ca, 15 % C, 35 % Έ (chemically pure) »

In steel foil bag tightly packed and in molten steel inserted mixture - 16ΟΟ + 5 ⁰ C.

^ 'Increase in % 0 and ppm Ή in molten steel due to addition of vanadium plus CaC ₀ or CaCIT _o mixture ("3 minV needle tube samples).

^x About 10 pounds of the metal leaked out of the oven due to the liveliness of the reaction.

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Table Y (Continuation) 0.20 % Ύ out % C too ^fy increase ^w Ir. V additional 3 v % 7 0.20 brought oven acceptance method ^; added 0.20 76 0.02 1 P 0.20 77 0.03 2 P 0.20 83 0.03 120 3 P 0.20 50 0.02 102 4 P 0.20 55 0.10 194 5 P ' 0.20 60 0.03 225 6 P 0.20 60 0.03 1 P 85 0.04 8th P 85 0.04 9 P

_ - λ r \

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Table YI comparison αer ^T 2 ° 3 Eigenschai ¹ C of V ₂ O, - reference property 4 * 87 ^Y 2 ° 5 1 density 1,970 ⁰ C 3.36 1 melting point black 690 ⁰ G 1 colour basic yellow 2 Character d. oxide 68 % Y + amphoteric (calculated ») composition -184 500 32 % 0 56 % ? + 44 % O 3  Free energy of education (1900 <> K) a ₀ = 5.45 cal / mole -202,000 cal / mol 4 crystal structure + 3 A a ₀ = 4.369 ± 5 A oC = 54 ° 49 ^f + 8 · b _Q = 11.510 + 8A Ehomboe drisch C ₀ = 3.563 + 3 A orthorhombisch

Claims (8)

3 9 A 8 O A - 18 - 60 704 12 12/10/82 Inventions An additive for adding vanadium to molten iron-based alloys, characterized in that it consists essentially of an agglomerated, blended mixture of about 50 to 70 mass% of finely divided VpO 2, and about 30 x 50 mass% of a finely divided calcium-bearing substance is selected from the group consisting of calcium-silicon alloy, calcium carbide and calcium amide-amide. 2. The additive according to item 1, characterized in that said VpO- has a particle size of predominantly 100 mesh and finer, and that said calcium-bearing material has a particle size of predominantly 8 mesh and finer, 3o additive according to item 1, characterized in that said calcium-bearing material is CaI cium silicone alloy. 4. The additive according to item 1, characterized in that said calcium-bearing material is calcium carbide, 5. The additive according to item 1, characterized in that said calcium-bearing material is calcium cyanamide, A process for adding vanadium to molten iron-based alloy, characterized in that an additive substantially consisting of an agglomerated, blended mixture of about, is immersed in the molten iron-base alloy QQ L 8 O U " ¹⁹ " 60 704 12 * "^^ 10.12.82 50 ... 70 Masseprosent feizxrerteiltain V ₀ Oo and about 30 ... 50 percent by weight of a finely divided calcium-bearing material "which is selected from a group consisting of calcium-silicon alloy, calcium carbide and Calciumzyanamid. 7, A method according to item 6, characterized in that said V ₀ OI has a particle size of predominantly 1-OO mesh size and finer and that said calcium-bearing material has a particle size of predominantly 8 mesh and finer. 8. The method according to item 6, characterized in that said calcium-bearing material is calcium-silicon alloy ' 9 »Method according to item 6, characterized in that said calcium-bearing material is calcium carbide. 10. A method according to point β, characterized in that e3 is calcium cyanamide in said calcium-bearing material.