Glass and Ceramics, Vol. 51, Nos.

1-2, 1994

ENAMELS
ADHESIVE STRENGTH OF HEAT-RESISTANT GLASS
CERAMIC COATINGS WITH NICHROME MELTS
A. P. Zubekhin, V. A. Zhabrev, and A. M. Kondyurin

UDC 666.11.01:548.5:691.629.004.8

The basic factor on which the operating properties of heat-resistant glass ceramic coatings are dependent is the strength
of adhesion of the coatings to the metal, primarily determined by the structure and phase composition of the metal-coating
transition layer.
There are many studies of the problem of adhesion of coatings to metals, but the essence of the processes that predetermine adhesion has not yet been sufficient elucidated. The following could be the most common factors whose effect on
adhesion can be considered sufficiently definite:
adhesion of coatings to metals is to some degree related to the degree of expansion of the surface of the metal [1];
the existence of oxide ftlms on the surface of the metals [1];
adhesion of coatings to metals is improved in the presence of bonding oxides (COO, NiO, MnO2, Fe20 3, Cr203) [2];
good adhesion of coatings to metals is usually observed when the TCLE of coating and metal are close [2].
The TCLE of the coating approaches the TCLE of the metal due to dissolution of the oxide film in the transition layer
during firing of the coating.
The effect of these factors on adhesion of metals to coatings is well known. However, in synthesis of glass ceramic
coatings based on complex silicate systems with a high concentration of iron oxides, the essence of the processes that take place
on the surface of the metal in formation of coatings has been insufficiently investigated. Studying the physicochemical
processes that take place in the metal-coating contact zone, i.e., in the transition layer, is especially important.
We investigated the effect of F%O 3 on the structure and phase composition of the nichrome alloy-glass ceramic
coating transition layer and the adhesive strength and properties of the coating as a function of the structure and phase
composition of the transition layer.
We previously established the optimum compositions of the glass matrices of heat-resistant glass ceramic coatings for
protecting nichrome alloys from high-temperature gas corrosion [3]. Martin slag in the amount of 27-30% (here and below,
the chemical and batch compositions are given in wt. %) of the following chemical composition was used as the basic batch
material in synthesis of the glass matrices: 19.7 SiO2, 6.3 A1203, 14.6 Fe203, 34.2 CaO, 17.3 MgO, 7.7 MnO 2, 0.2 loss on
calcination. The glass matrices contained 8, 12, and 16% F%O 3 (over 100%), since the amount of Fe203 in the slag varied
from 13 to 20%. The compositions of frits of the heat-resistant coatings are reported in Table 1.
The frits were melted in alundum crucibles in a Silit electric furnace at 1250~ for 2 h with rapid cooling in air. After
melting, the flits were ground in a ball mill and passed through a No. 0063 sieve. The slips had the following composition
(%): 50 frit, 5 Chasov Yar clay, 45 water.
The electrolyte was 0.2% Na2B407 (over 100%). The slips were aged for 2 days, after which they were deposited
on KhN78T and Kh18N10T alloys by dipping. The samples with the applied and dried coatings were ftred at 1150~ for 3
min. The samples were treated with heat at 890~ for 15 min to create the microcrystalline structure of the coatings.
The adhesive strength with nichrome alloys and the TCLE, heat resistance, and thermal stability were determined to
fred the optimum composition of the coatings (Table 2).
The percentage of chips in the coating was significantly higher than the percentage of chips to the metal in testing the
coatings for the strength of adhesion to the support. The adhesive strength of coating 3 was higher than for coatings 1 and 2.
We can probably hypothesize that the transition layer between alloy and coating has an important effect on adhesion of the
support to the coating (the percentage of chips to the metal was 2.5-8 times lower than over the coating).
Novocherkass State Technical University; Institute of Silicate Chemistry, Russian Academy of Sciences. Translated
from Steklo i Keramika, No. 2, pp. 25-28, February, 1994.
0361-7610/94/0102-0(785512.50

Plenum Publishing Corporation

85

TABLE 1
Frit

Concentration, wt. %

S~02 'A1263

cao

MgO

Na20

K20

38,2
19,1
37,0
18,5
36,0 I 18,0

19,1
18,5
18,0

3,S
3,7
3,5

6,1
5,9
5,7

5,3
5,2
5,0

IF~O8
6,1
8,9
11,5

MnO 2

2,3
2,2
2,1

*The sum of the oxides in all versions is 100%.

46~g

A 2~',o~

/!9
Fig. 1. Diffraction patterns of the transition layer of coatings 1, 2, and 3. A: Helenite;
*: okermanite solid solutions; x: Cr203; [3: NiO; *: Fe203; o: FeO; I1: Fe.

The TCLE of the transition layer approached the TCLE of the support (TCLE of nichrome alloys is 160" 10"7-170910-7
K-I) due to its saturation with Cr 3+, Fe 3+, and Ni2+ ions. In addition, the degree of crystallinity of the glass matrices of the
coatings increased with an increase in the.concentration of F%O 3 in them [3]. In our opinion, all of this increases the stren~th
of adhesion of the coatings to the support and consequently improves their technological characteristics.
The structure and phase composition of the alloy-coating transition layer were investigated to determine the strength
of adhesion of the coatings to the nichrome alloys.
The study was conducted by x-ray phase analysis (XPA) and x-ray structural microanalysis (XMA).
The analysis of the diffraction patterns (Fig. 1) shows that helenite, 2CaO.A1203.SiO2, and chromium-iron-containing
okermanite solid solutions, 2CaO.(Cr, Fe)203-MgO-2SiO2, are the basic phases constituting the alloy-coating transition layer.
The intensity of the maxima corresponding to these phases increases with an increase in the concentration of Fe203 in the glass
matrices. This suggest an increase in the degree of crystallinity of the coatings due to an increase in the concentration of
helenite and okermanite solid solutions. The transition layer also contained a small amount of Cr203, NiO, Fe203, FeO, and
Fe (traces).

86

TABLE 2
coating

Index

2
Strength of adhesion to alloy in deformation at a
depth of ,7 mm, % chips:
to the metal
over the coating TCLE of coatings
initial
crystallized
Heat resistance (increase in
weight at 900~ after 100 h
of holding), % chips
Thermal stability (at 900-20~
with cycling for 4 h after
100 h of holding), % chips
to the metal
over the coating

coating

,2

10

27

10

15,

116
125

117
140

110
135

2,5" 10 -5

2,4-10-5

2,0-10-5.

25

tO.

alloy

.-=

~o

~.

~;~o .... q~b-'

~bo

~-:--)~o-=-~

I
1

Fe

--2o

....... dS

'

~bo

'

~a

'

480

'

2'eO

2~ Distance, lzm

Fig. 2. Intensity of characteristic radiation of Cr, Fe (a) and Ni, Si (b) in the transition
layer of the coatings.

87

coating

alloy

N[

S'

2
._=

N;
....
20

Sc

I
c;o ....

q'oo

J~o

~go

~2o

N~
21)

~'6o

3oo

S;
~o

~bo

~o

~8o

29o

Distance,/~m

Fig. 2. Continued.

The hypotheses based on the XPA data were confu-med by studies of the distribution of silicon, iron, chromium, and
nickel in the transition layer by XMA (Fig. 2). A non-monotonic change in the intensities of the characteristic radiation of
silicon, iron, and chromium was observed in the transition layer. On the contrary, the change in the intensity of radiation of
nickel was monotonic. This indicates that silicon, iron, and chromium form compounds of defined composition. The
coincidence of the extremes of the intensities of radiation of Fe and Cr probably indicates that they are present in one compound
and play the same role in it, i.e., they are in a similar crystal chemical state. These results are in complete agreement with
the XPA data. According to the XPA data, nickel does not form compounds with other cations and exists as NiO, which is
reflected in the monotonic character of the change in the intensity of its radiation.
An increase in the concentration of Fe203 in the transition layer together with Cr203 thus increases the degree of
crystallinity of the coatings due to the formation of helenite and okermanite solid solutions as the basic crystalline phases. The
crystals formed have the shape of grains and are strongly joined with the residual glass phase. The glass phase serves as an
adhesive constituent between metal and microcrystals [4]. This increases the adhesive strength of these coatings with the
nichrome alloys as their crystallinity increases.
The formation of a nichrome melt-glass ceramic coating transition layer can arbitrarily be divided into two basic
stages:
formation and subsequent dissolution of the oxide film of the alloy and further oxidation of the alloy under the melt
of the coatings due to both grid oxygen and atmospheric oxygen which diffuses through the melt;
crystallization of the coating on repeated heat treatment.
88

In the metal-glass-forming melt system, dissolution of the oxide fflm is limited by either feed of the substance or
recombination of atoms and molecules [5]. On repeated heat treatment, crystalline phases containing components of the support
and the coating are formed in the transition layer, and this determines the adhesive strength of the coatings with the metal
For the coatings investigated, we can thus hypothesize the following mechanism of formation of the nichrome-coating
transition layer.
Cr203 and Fe203 contained in the oxide film in the coating melt are dissolved in the reaction of the melt with the
nichrome alloy. Cr203, Fe203, and NiO are subsequently simultaneously formed on the surface of the metal due to the oxygen
in the melt and the oxygen diffusing from the air. These processes are limited by the structure and viscosity of the melt and
the mobility of the Cr 3+, Fe 3+, and Ni2+ ions. Cr 3+ ions have the highest mobility, and the melt in the transition layer is
consequently saturated with them to the greatest degree, confa-med by the XMA data [5].
For this reason, we can hypothesize the following: the Cr203 in the transition layer, like Fe203 in the structure of
the melt and oxide film, cause the formation of microheterogeneities in the melt. Regions enriched with [CrO4] 5 - , [FeO4] 5 - ,
and [A104] 5- groups appear, and the concentration of [CRO415- increases in approaching the metal-coating interface. The
following equilibrium reactions take place:
[Cr0415-+ 0 2- ~- [Cr0619-;
[Fe04] s- + 0 2- ~ [Fe0619-;

[hlO4] s- + 02- ~ [A106]9-.

The third of these reactions compensates for the fin:st two, since they are all interrelated
[FeO4] s- + [CrO4] 5- +

+ [A10619- Z [A104]s- +

+ [reo,?- + [cro619-.
An increase in the concentration of Fe 3 + and Cr 3 + in the melt shifts this equilibrium to the right, which stabilizes the
AI3 + ions in four coordination. This causes separation of the melt into regions in which [SiO4]5- and [A104] 5 - groups act
as glass-forming agents and regions with a high concentration of [FeO4] 5 - and [CrO4.]5 - as glass-forming agents. As the equilibrium shows, a shift to the right, which decreases the coordination of A13+, should worsen the crystallization power.
However, this does not take place due to the simultaneous increase in the coordination of both Fe 3 + and Cr 3 +, which also
causes increased crystallization of the coating with formation of helenite and okermanite solid solutions.
Chromium is probably present in the melt in the trivalent state, since we know that Cr3+ is more stable than Cr 6+ at
high temperatures and in acid medium. However, oxidation of metallic chromium during dissolution can cause the Fe 3 + --,
Fe 2+ ---, Fe~ transition according to the reactions:
3Cr ~ + 2Fe 3+ = Cr 3+ + 3FJ+;
3Cr ~ + Fe 2+ = Cr 3+ + 2Fe ~
Traces of metallic iron were detected in the transition layer by XPA and XMA.
The chemical properties of iron and chromium are correlated with their position in the periodic system [5]. Their
proximity could indicate the similarity of the properties in the structure of the glass and the transition layer of heat-resistant
coatings.
The chromium, like the iron, in the transition layer thus acts as a catalyst of crystallization and is not its center.
Our studies established the optimum composition of a heat-resistant glass ceramic coating for protecting nichrome alloys
from high-temperature gas corrosion. Martin slag was used as the basic batch material to decrease the cost of the coating and
utilize wastes. A mechanism was proposed for the formation of the alloy-coating transition layer, and the dependence of the
adhesive strength and properties of the coatings on the structure and phase composition of the transition layer was demonstrated.

89

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,

2.
3.

5.

90

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