United States Patent (19) 11) 4,050,957

Sales (45) Sept. 27, 1977

54 PROCESS FOR THE PASSIVATION OF 56 References Cited
FERROSILICON U.S. PATENT DOCUMENTS
75) Inventor: Maurice Sales, Ville Longue, France 2,050,305 8/1936 Frey et al............................. 148/10
2,110,717 3/1938 Sellers ......... ... 148/6.14
73) Assignee: Societe Pyreneenne du 2,873,512 2/1959 Robinson ............................ 29/182.5
Silico-Manganese, Paris, France 3,169,851 2/1965 Fleming, Jr. et al........... 148/6.35 X
(21) Appl. No.: 620,742 FOREIGN PATENT DOCUMENTS
395,148 6/1938 Canada
22 Filed: Oct. 8, 1975 1,245,680 7/1967 Germany ............................ 148/6.14
Primary Examiner-Ralph S. Kendall
Related U.S. Application Data Assistant Examiner-Charles R. Wolfe, Jr.
(63) Continuation of Ser. No. 345,468, March 27, 1973, Attorney, Agent, or Firm-Cushman, Darby & Cushman
abandoned, which is a continuation of Ser. No. 52,879, (57) ABSTRACT
July 7, 1970, abandoned.
A process for the passivation of discrete particles of
(30) Foreign Application Priority Data ferrosilicon containing 30-90% by weight silicon com
July 10, 1969 France ................................ 69.23581 prises contacting the particles with a gaseous oxidizing
agent at a temperature between 800-1150' C for a time
51 Int. Cl2 ..... as a a a a as a so as so a C23C 11/00 ranging between 1-12 hours. The treated particles can
52 U.S.C. .................................... 148/6.3; 148/6.35; be admixed with a binding agent to form a paste which,
148/105; 148/110; 148/113; 427/216 in turn, is used as a coating for shielded arc electrodes.
58) Field of Search ................. 148/6.35, 6.3, 24, 104,
148/105, 110, 112, 113; 427/59, 215, 216 5 Claims, 1 Drawing Figure
U.S. Patent Sept. 27, 1977 4,050,957

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1
As shown in the figure, the apparatus comprises a
PROCESS FOR THE PASSIVATION OF vessel 1 made of stainless steel which is disposed in a
FERROSLCON furnace 2 furnished with a grilled bottom 3, below
which there is provided gas intake 4. The grill 3 is sur
This is a continuation, of application Ser. No. 345,468 5 mounted by a layer 5 of crushed and amalgamated re
filed Mar. 27, 1973, now abandoned which is a continua fractory material, which can be, for example, alumina,
tion of Ser. No. 52,879, filed July 7, 1970, now aban corundum or "Inox Poral” steel. Above the said layer 5,
doned. the powdered ferrosilicon 6 is introduced and brought
The present invention relates to a new process for the O
to the desired temperature at the same time that gas is
passivation of ferrosilicon and, more particularly, to the admitted via intake 4 under sufficient pressure to effect
treatment of discrete ferrosilicon particles with an oxi suspension of the particles of ferrosilicon. The flow of
dizing agent, the thus treated ferrosilicon particles being gas passes vertically through grill 3, layer 5 and fluid
advantageously employed in a coating composition for ized bed 6 and is vented to the outside through port 7 in
shielded arc electrodes. 15 cover 8.
Heretofore, ferrosilicon containing 30 to 90% by The efficiency of the process of the invention is dem
weight silicon, has been used in a powdered form to onstrated by the two following tests.
gether with a binder such as an alkaline silicate to pro
vide a coating composition for shielded arc welding TEST NO. 1
electrodes. In a glass tube 18 mm in diameter and 150 mm long,
However, it has been observed that ferrosilicon in the 20 there is introduced 2 g of the powdered ferrosilicon and
presence of an aqueous alkaline solution and particu 14 cc of an aqueous solution of sodium silicate obtained
larly an aqueous alkaline silicate, gives rise to a reaction by dissolving two parts by volume of sodium silicate (at
accompanied by the release of hydrogen, which disad 47 Be SiO/Na2O = 2.9) in one part volune water, and
vantageously causes cracks in the resulting coating on 25 the whole is brought to a temperature of 90' C. The gas
the welding electrodes. which is released is collected in a eudiometer.
In an effort to obviate this disadvantage, it has been
proposed to use atomized ferrosilicon particles, rather TEST NO. 2
than powdered ferrosilicon since such particles are In a 50 cc Erlenmeyer flask there is introduced a 25g
spherical in form, having, consequently less total sur 30 sample of ferrosilicon and 25 cc of a 10% potassium
face area, which thereby limits the intensity and the
extent of the reaction with the aqueous alkaline solu hydroxide solution. The whole is placed in a thermostat
tion. It has also been proposed, in an effort to avoid a at 50' C and the release of gas is measured.
reaction of the ferrosilicon with the alkaline media, to The amount of gas released, noted in both of these
subjec the ferrosilicon to a pre-treatment comprising 35 tests, allows, by comparison with an untreated alloy
contacting the ferrosilicon particles with an aqueous sample, the judgement of the degree of passivation of
solution of an alkaline hydroxide, along or with an the treated metal.
alkaline earth permanganate or dichromate, washing The following table indicates the results obtained
the thus treated ferrosilicon with water and drying the with different samples of 45% ferrosilicon having a
same. However, none of the proposed treatments have particle size less than 0.210 mm, which samples were
provided a satisfactory reduction of the release of gas subjected to the conditions of test No. 1.
which is produced when the ferrosilicon is contacted
with an aqueous alkaline solution. Gaseous Volume collected
It has now been found that the release of such gas at the end of
produced when ferrosilicon particles are contacted 45 Sample 30 mins 1 hr. 2 hrs 4 hrs
with alkaline solutions can be substantially eliminated Untreated ferrosilicon 50-60 cc - --
or minimized if the powdered ferrosilicon, having a Ferrosilicon particles
particle size less than 0.3 mm, is subjected to an oxidiz treated at 850 C with
oxygen for 12 hours 2 cc 4 cc 12 cc
ing treatment at a temperature between 800 and 1150' C Ferrosilicon particles
for a period of time ranging between 1 to 12 hours, said treated at 900 C with
duration being a function of the temperature and of the oxygen for 10 hours
Ferrosilicon particles
2 cc 3 cc 8 cc
nature of the gaseous oxidizing agent which is used. treated at 1100' C with
The said oxidizing agent can be air, oxygen, steam or oxygen for 2 hours 2 cc 2.5cc 6 cc
carbon dioxide and, if desired, it can include a gaseous
inorganic acid, such as hydrochloric acid in amounts 55 A sample of particles having essentially the same
ranging from about 5 to 15 weight percent, based on the dimensions were subjected to test No. 2, and at the end
total weight of the gaseous oxidizing agent. of one hour of contact with the potassium hydroxide
When air or oxygen is used as the oxidizing agent, it solution, yielded the following results for comparison.
is sufficient to treat the ferrosilicon for 2 hours at 1100
C to attain excellent passivation, whereas as 850' C it is
necessary to continue the said treatment for 12 hours. Sample Volume of Gas Recovered
The treatment of ferrosilicon with the oxidizing agent Untreated ferrosilicon 23 to 35 cc
can be effected in any suitable apparatus such as a rotary Ferrosilicon treated at
850 C with air for 3 to 5 cc
furnace, a plate furnace, or any other furnace which 12 hours
permits heating of a powder at high temperature while
maintaining intimate contact between the said powder
and a gas. Preferably a fluidized bed technique is used in The following example describes a method of carry
an apparatus shown in the accompanying drawing. ing out the process of the present invention.
 3
4,050,957 4.
EXAMPLE served in the coatings made with untreated ferrosilicon.
The paste can be produced by admixing the treated
Into a vertical cylindrical furnace, 85 cm in diameter ferrosilicon particles with about 5 to 40 weight percent
and 1.30 m high, there is placed a charge of 1300 kg of of a binding agent comprising an aqueous alkaline sili
powdered ferrosilicon which contains 44.9% silicon, 5 cate solution, based on the weight of the ferrosilicon
75% of the said particles have a dimension ranging particles. The core of the electrode, can, of course, be
between about 0.250-0060 mm. The charge is fluidized made of any conventionally employed metal or carbon
for 12 hours at 850 C using a jet of air compressed at and the electrode size can also be one which is conven
1.2 bars and at a flow rate of 5 m3 per hour. The particle tionally employed, for instance, one having a size rang
size of the charge was not modified after cooling. Sam O
ing from about 1/16 to 5/16 inch.
ples of the thus treated ferrosilicon were subjected to What is claimed is:
tests 1 and 2 described above as were equal samples of 1. A process for the passivation of discrete particles of
essentially the same, but untreated, ferrosilicon parti ferrosilicon containing 30 to 90% by weight silicon
cles.
The following results were observed: 15 comprising contacting said ferrosilicon particles with a
gaseous oxidizing agent containing a gaseous inorganic
acid, said gaseous oxidizing agent being selected from
Test No. 2 the group consisting of air, oxygen, steam or carbon
Test No. 1 Gas Volune
Gas volume collected
at the end of
collected at
the end of
dioxide, at a temperature between about 800' and 1150
Sample 1 hr. 2 hrs 4 hrs hour
C for a period of time ranging between about one and
twelve hours.
Untreated ferro
silicon alloy 136cc - 28 cc 2. The process of claim 1 wherein the inorganic acid
Treated ferrosilicon 0.5 cc 4 cc 9 cc 4 cc is hydrogen chloride.
3. Ferrosilicon powder obtained in accordance with
The ferrosilicon particles treated according to the 25 the process of claim 1.
process which is the subject of the present invention can 4. A paste for coating welding electrodes comprising
be used for making coating pastes, particularly for a mixture of ferrosilicon particles produced in accor
welding electrodes. These pastes, obtained by impreg dance with claim 1 and an aqueous solution of an alka
nation of the powdered ferrosilicon with an aqueous line silicate.
solution of alkaline silicates, provide the extremely ad 30 5. A welding electrode coated with a paste compris
vantageous property of not giving rise to a substantial ing a mixture of ferrosilicon particles produced in ac
release of hydrogen in the course of their preparation. It cordance with claim 1 and a binding agent comprising
follows that the coating which is obtained does not an aqueous solution of an alkaline silicate.
present troublesome cracks or fissures which are ob 35

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