P1: KCU/SRK P2: KCU/TKL P3: KCU/TKL QC:

Journal of Sol-Gel Science and Technology KL454-11-Gilath May 23, 1997 11:46

Journal of Sol-Gel Science and Technology 10, 101–104 (1997)

°
c 1997 Kluwer Academic Publishers. Manufactured in The Netherlands.

Water Repellent Coating for Welding Electrodes Based

on Sol-Gel Technology

IRITH GILATH
Soreq NRC, Yavne 81800, Israel

Received March 29, 1996; Accepted October 23, 1996

Abstract. Silicone resin coatings prepared by the sol-gel method were applied on welding electrodes to protect
them against water absorption during storage or transportation. The performance of the electrodes was tested by
measuring the free and total water content of the weld. The total water content of the coated electrode was just
slightly above the permitted level (<0.2%) due to the organic part of the silicone resins that decomposes during
welding liberating a very small quantity of water.

Keywords: sol-gel coatings, incineration, welding electrodes

1. Introduction coating. Several water repellent silicone resin coatings

were tested to reduce water absorption and improve the
Welding electrodes are made of a wire and a ceramic shelf life of the electrodes.
coating made of inorganic salts namely silicates of al-
loying metals. The ceramic coating of the electrode is
2. Electrode Production and Quality Control
absorbing humidity due to its porosity. To assure good
welding, the electrodes must be dry, with a water con-
Some 200 types of electrodes including MIL-Specs
tent less than 0.2% [1]. Even for very low water content,
for welding different metals are marketed, containing
during the high welding temperature, the residual water
about 150 different inorganic salts mainly silicates to
is decomposed to hydrogen and oxygen. The hydro-
provide the alloying elements contained in the ceramic
gen is readily absorbed by the melted metal during the
coating. The silicate powders are transformed into a
welding forming metal hydrides. The metal hydrides
paste using aqueous solution of potassium silicate (wa-
are brittle and greatly reduce the mechanical properties
ter glass) as binder. The paste is extruded around the
of the welded parts. A very low water content is crucial
centered wire. The electrodes are dried on trays and
for quality weldings especially for installations oper-
sintered in oven for several hours, and packed [1].
ating at low temperatures such as oil drillings in the
Electrode samples from every batch undergo several
North, ships, etc., where the low temperatures induce
tests, the most important being residual water, weld-
additional metal brittleness and eventual mechanical
ability and hydrogen absorbed in the weld.
failure.
Low hydrogen electrodes are obtained by drying and
sintering at 300◦ C and packing under vacuum. The low 3. The Silicone Resin Coating
hydrogen electrodes represent about 40% of the total
welding electrodes world market and their demand is The sol-gel reaction is a synthetic route by which silane
increasing [1]. alkoxides are transformed to glassy materials by a se-
Silicon polymers can be prepared by the sol-gel quence of hydrolysis and condensation reactions [2, 3].
method and easily applied as a thin inexpensive The hydrolysis stage involves reaction with water, that
P1: KCU/SRK P2: KCU/TKL P3: KCU/TKL QC:
Journal of Sol-Gel Science and Technology KL454-11-Gilath May 23, 1997
102 Gilath
Table 1. Properties of commercial silicone resins.
Silicone resin Type of resin Hardness
Silres KX Methyl silicone Hard
Silres HK 46 Methyl silicone Hard
Silres REN 50 Methyl phenyl silicone Medium hard
Silres REN 60 Methyl phenyl Medium hard
Silres MSE 100 Polymethyl methoxy Very hard
is catalysed by acid or base and formation of alcohol.
The condensation stage results in the formation of
siloxane macromolecules. The fast sol-gel employs
methyl-substituted alkoxysilane monomers [3]. Dur-
ing the heating, when hydrolyzation and polymeriza-
tion takes place, the alcohol is evaporated but some
traces of water may be incorporated in the polymer net-
work. The polymer obtained is a viscous liquid which
is transformed into a transparent solid by curing. Sili-
cone resins are easily applied in liquid form and dried
and cured at room temperature or higher, up to 200◦ C
[2, 3]. They adhere very well to glass and silicates.
The above properties seem to be suitable to apply a
hydrophobic coating on welding electrodes.
The pyrolysis (incineration) of methyl silicone resins
with the empirical formula CH3 SiO3/2 produces sili-
con dioxide, carbon dioxide and water. About 100 g
methyl silicone resin will produce about 90 g silica af-
ter complete incineration without smoke. This high
ash content of silica assures very low water contami-
nation of the ceramic when coated with silicone resins.
Several silicone resins were tried in order to find the
most suitable material for coating. The resins differ
by monomers, viscosity and solvent. These proper-
ties influence on the thickness and quality of the coat-
ing, its porosity, determine residual water content and
hydrophobicity.
4. Experimental
The fast sol-gel silicon resins were prepared according
to US Patent no. 5,272,240 (1993), see Ref. [3]. Methyl
trimethoxy silane (MTS from Aldrich) was mixed and
hydrolized with water containing 0.01 M HCl (1 : 1.8
mole ratio). It polymerised at ∼80◦ C and a viscous
liquid silicone polymer was obtained in a few min-
utes. The viscous liquid was applied directly on the
electrodes by dipping. The drying and curing of the
11:46
Solid content Viscosity
Appearance % Solvent mPa.s
Clear soln 50 Xylene 6–12
Clear soln 50 Xylene + butanol 4 : 1 40–60
Clear soln 50 Xylene + butanol 9 : 1 160
Clear soln 60 Xylene 60
Clear soln 100 Solvent free 25–35
coating was performed at room temperature for one
day, or two hours at 80–100◦ C.
The water content was measured with a Mettler
DL37 instrument based on the Karl Fischer method.
The water measurement range of the Mettler DL37 is
10 µg to 100 mg water content/sample with a limit of
detection of 0.1 µg water. The samples for water con-
tent were prepared as follows: a) the ceramic part of
the electrode was crushed and a weighed sample was
introduced in the oven of the Mettler DL37 for wa-
ter determination, b) procedure a) was repeated for a
sol-gel coated electrode. The water content of the coat-
ing material (silicone polymer) was also determined in
liquid and solid form after drying and curing.
Coloured coatings were easily obtained by incorpo-
rating fluorescein or rhodamine 6G at 0.001M concen-
tration in the silicone polymer. The purpose of coloured
coatings was to obtain colour coding for the electrodes,
as an alternative for the method used today, where pig-
ments are mixed into the silicates before extruding.
Commercial silicone resins, which are binders for
heat resistant paints, were obtained from Wacker [4].
These resins are also based on methyl or phenyl sil-
icones with or without solvents and have different
viscosities. The following resins were tried for water
repellent coatings, see Table 1.
The free and crystalline (total) water content was
measured by the Karl-Fisher method. The free water
was measured at 200◦ C oven temperature and the crys-
talline water was obtained at 500◦ C.
5. Results
The total water content of the electrodes before coat-
ing was 0.11–0.19%. Several batches of electrodes
(each batch containing 85 electrodes) were coated
with different resins as described in the experimen-
tal section. The resin uptake was 0.75–1 ml/electrode
P1: KCU/SRK P2: KCU/TKL P3: KCU/TKL QC:
Journal of Sol-Gel Science and Technology KL454-11-Gilath May 23, 1997 11:46

Water Repellent Coating 103

Figure 1. Surface of a silicone polymer coating (sol-gel) by atomic force microscope.

corresponding to about 0.1 ± 0.03 mm coating thick-
ness. All polymers had excellent adherence to the ce-
ramic coating of the electrodes and a shiny and uniform
appearence, see Fig. 1. The surface of cured sol-gel sil-
icon polymer is very smooth, therefore an atomic force
microscope was used instead of a scanning electron
microscope.
Uneven and bursted coatings were obtained only
when cured at too high temperatures (above 200◦ C)
in unsuitable ovens. The total water content of the fast
sol-gel coated ceramic, as measured by the Karl-Fisher
method, was 0.7% which was unacceptable for weld-
ing electrodes. The high water content was a result of
the residual water from the hydrolysis of MTS, which
was absorbed in the ceramics and trapped by the drying
polymer film.
As can be seen in Table 2, the free water, measured
at 200◦ C oven temperature, is very low. The small
quantity of resin needed (∼1 gr per electrode), will
increase the initial free water content of the electrode
by no more than 5%. However the total water content
of the commercial silicone resin coated electrode was
0.24% or higher, which is above the permitted level.
The higher water content was due to the decomposi-
tion of the organic part of the silicone resin at 500◦ C,
as measured by differential scanning calorimetry. At
this temperature the organic moieties are burnt to car-
bon dioxide and water, therefore the methyl or phenyl
groups contribute to the total water content.
Part of the water in the silicon polymer is decom-
posed during the high welding temperature to hydrogen
and oxygen. The hydrogen is absorbed in welds as
metal hydrides which are responsible for the hydro-
gen embrittlement. This result was confirmed also by
the hydrogen measurement in the experimental welds.
For 0.24% total water content, the measured hydrogen
in weld was 17–18 ml/100 gr weld, which is higher
than the 15 ml maximum allowable value [1]. By
reducing the coating thickness with solvents and, at
the same time the total water content respectively, the
porosity of the coating is increases during the evap-
oration of the solvent and the mechanical strength of
the film is reduced. Therefore, this is not a practical
solution.
6. Conclusions

Table 2. The free water content of liquid commer- Different silicone resin coatings were tested as poten-
cial silicones and cured solid form.
tial water repellent coatings for welding electrodes.
Resin HK 46 REN 50 KX MSE 100 Very good and uniform coatings were obtained with
Liquid 1.06% 0.25% 0.88% 0.4% all silicone resins tested. The coatings were obtained
Solid 0.295% 0.286% 0.183% —
by simply dipping the electrodes in the liquid resins.
The drying and curing of the coatings were performed
P1: KCU/SRK P2: KCU/TKL P3: KCU/TKL QC:
Journal of Sol-Gel Science and Technology KL454-11-Gilath May 23, 1997
104 Gilath
in air. For a 0.1 mm coating thickness we used about
0.75–1 ml/electrode. The low price of silicone prod-
ucts and their excellent adherence to the ceramic sili-
cates of the arc welding electrodes made them attractive
candidates for improving the shelf life of arc welding
electrodes. The total water content of the coated elec-
trode was just slightly above (0.05–0.1%) the permit-
ted level due to the organic part of the silicone resins
which decomposes completely at the arc welding tem-
perature (above 2000◦ C) and produces water, silicon
dioxide and carbon dioxide. At welding temperatures
the water decomposes to hydrogen which is absorbed
in the welds as metal hydrides. Therefore the benefit
of the water repellent coating on welding electrodes is
limited.
11:46
Acknowledgment
The electrode samples were provided by ZIKA Elec-
trode Works Ltd., Acre, Israel. The technical discus-
sions with the R&D group is greatly appreciated.
References
1. ZIKA Electrode Works, Private communications.
2. Sol-Gel Technology for Thin Films, Fibers, Preforms, Electron-
ics and Specialty Shapes, edited by L.C. Klein (Noyes Publ., N.
Jersey, 1988).
3. Y. Haruvy and S.E. Weber, Fast sol-gel preparation of glasses, US
Patent No. 5,272,240 (1993).
4. Wacker Technical Bulletin: SILRES silicone resins for heat-
resistant paints.