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Journal of the UniversityY.ofTumbaleva, D.

Chemical Technology L. Fachikov
Metallurgy, 46, 4, 2011, 357-362


Y. Tumbaleva, D. Ivanova, L. Fachikov

University of Chemical Technology and Metallurgy Received 25 July 2011

8 Kl. Ohridski, 1756 Sofia, Bulgaria Accepted 20 September 2011


The paper presents a continuation of the investigation on the production and characterization of crystalline zinc
phosphate coatings on carbon steels and cast irons in solutions of a newly developed high speed phosphating composi-
tion, KAF-101 ZT. Gravimetric, X-ray structure and transmission electron microscope methods are used to determine the
effect of P2O5 and NO3-ratio on the thickness/mass of the produced coatings, their phase composition and structure. The
tests are carried out in 15 % by volume solutions of the phosphating composition and P2O5:NO3- ratios 1:1.80; 1:3.12 and
1:7.06, respectively. The working solutions temperatures are 50 and 70oC and the duration of the phosphating process
3 to 18 min.
Keywords: phosphating, zinc phosphating, carbon steels.

INTRODUCTION quite wide - usually 1-3 % NO 3- in the working solu-

tion. The acceleration degree in zinc phosphating by
The acceleration of film formation in the ferrous nitrates could be expressed more conveniently by the
carbon alloys phosphating could be achieved by adding ratio P2O5:NO3-. At higher NO 3- content the phos-
to the phosphating solution of electropositive than iron phate coating formation time is shorter but at the
metals (copper, silver, nickel, cobalt, gold, platinum, etc.) same time their final mass/thickness decreases. The
and oxidizers (nitrates, nitrites, chlorates, peroxides, etc.) slime formation for coating unit mass decreases with
or by physical means (spray deposition, brushes, rotating increase of NO3- content in the phosphating solution
disks, etc.). Besides an acceleration of the coating forma- [2, 5].
tion, some of the accelerators oxidize Fe+2 ions in the
phosphating solutions, transform them in insoluble com- EXPERIMENTAL
pounds and thus, decrease their damaging effect on the
coatings. Other accelerators refine the structure and lead Materials and samples
to fine crystalline coatings formation [1-4]. The test samples are made of sheet low carbon
The nitrates, alone or in combination with other steel (0.17 % ) with 1.0 mm thickness. For gravimet-
accelerators, are widely used in the zinc phosphating ric tests the sample area is 5.10-3 m2, and for the physi-
baths. The nitrate acceleration concentration range is cal methods 1.10-3 m2.

Journal of the University of Chemical Technology and Metallurgy, 46, 4, 2011

Table 1. Experimental conditions.

Concentration, Temperature, Ratio
% by volume P2O5:NO3
KAF-101 ZT 15.0 50.0; 70.0 1:1.80
KAF-101 ZTB 15.0 50.0; 70.0 1:3.12
KAF-101 ZTC 15.0 50.0; 70.0 1:7.06
The preparation of the samples is described in phosphate coating mass/thickness, the coating is removed
details earlier in [6]. from the surface of the samples by dissolving in hydro-
Solutions chloric acid with an inhibitor. There follows washing, dry-
The phosphating media are water solutions of ing and weighing of the samples (m3, g; 0.0002 g). From
the composition KAF-101ZT that contains free phos- the values of m1, m2 and m3 the phosphate coating mass/
phoric acid, monosubstituted zinc phosphates as well thickness 1, the dissolved quantity of the substrate metal
as stabilizers, accelerators, etc. The Table 1 presents 2 and the change of the mass of the working sample
the conditions under which the tests are performed. during its phosphating 3 are determined [6].
These conditions are determined in our earlier
investigations [7]. RESULTS AND DISCUSSION

Research methods Fig. 1 shows the change of the mass/thickness of

the phosphate coatings 1 in solutions with different
Gravimetric method P2O5:NO3- ratios, at two temperatures (50 and 70oC).
The method is already used in the study on the The dependences show that for all P2O5:NO3- ra-
kinetics of formation and growth of phosphate coatings tios, phosphate coatings of greater mass/thickness are
depending on the effect of various factors. It is described formed at the lower temperature 50oC. With increase
in details in [6]. of the P2O5:NO3- ratio the mass/thickness of the phos-
X-ray structure analysis phate coatings decreases for both temperatures. At ratio
The phase composition of the phosphate coat- of P2O5:NO3- = 1:7.06 the temperature effect on the phos-
ings is determined by X-ray analysis. The investigations phate coating mass/thickness is less expressed which could
are carried out on apparatus TUR-M-62 with source be explained by the greater nitrates content in this case,
Cu K, 600/1o. which dominates in the phosphate film formation.
Transmission electron microscopy (TEM) Fig. 2 presents how the substrate dissolved metal
The morphology of the phosphate coatings is stud- mass varies in the process of phosphate coating forma-
ied by the method of the two-stage replicas using EM- tion. The courses of the curves show that the dissolved
400 Philips apparatus. metal quantity grows both with the phosphating time
and increase of the P2O5:NO3- ratio. This pattern, with
Method of work the exception of the highest ratio, is retained at both
The specified volume of KAF-101ZT phosphat- temperatures of the phosphating solutions.
ing concentrate is diluted with the necessary quantity of Fig. 3 illustrates the change of the samples masses
water and tempered to the preset temperature. The pre- in the process of their phosphating 3. It follows from the
pared in advance and weighed by an analytical balance figure that only at the lowest ratio of P2O5:NO3- = 1: 1.80
(m1, g; 0.0002 g) samples are immersed in the solu- the mass of the phosphated samples is greater than their
tion. After the expiration of the phosphating time the initial mass. For the other two ratios the dissolved quan-
samples are taken out of the solution, washed with run- tity of metal exceeds the mass of the phosphate coat-
ning water and dried by hot air. ings. These results provide the possibility to specify the
The phosphated samples are weighed by analytical optimum conditions of the most economical and effec-
balance (m2, g; 0.0002 g). In order to determine the tive phosphating of carbon steel products.

Y. Tumbaleva, D. Ivanova, L. Fachikov

The X-ray phase analysis of the produced phos- range (length 2-20 m and thickness 0.5-3 m). The
phate coatings (Fig. 4) shows that irrespective of the phosphate coating produced at the highest value of the
proportion P2O5:NO3-, the coatings consist of two phases: P2O5:NO3- ratio (Fig. 5 c) has also homogeneous structure
hopeite, Zn3 (PO4)2.4H2O and phosphophyllite, Zn2Fe but contains mainly agglomerated, elongated crystals of
(PO4)2.4H2O. dimensions: length 10-20 m and thickness 1.5-2 m.
TEM micrographs of zinc phosphate coatings
prepared in solutions of different P2O5 : NO3- ratios are CONCLUSIONS
presented in Fig. 5. For the lowest value of the P2O5:NO3-
ratio (Fig. 5 a), the structure is heterogeneous and con- The results in this paper related to the study of
tains micro-sectors in which two types of crystals are the effect of the P2O5:NO3- ratio on the production of
dispersed: elongated (length up to 10 m, thickness 1-3 zinc phosphate coatings lead to the following more im-
m) and crystalline aggregates with close to cubic shape portant conclusions:
(5x5 m). When the NO3- content in the solution is the mass/thickness of the phosphate coatings
increased (Fig. 5 b) the structure is homogeneous but decreases with the increase of the NO3- content in the
the dimensions of the elongated crystals vary in a wider phosphating solutions;

Fig. 1. The effect of phosphating time, on the mass of the phosphate coating, M1: a KAF- 101ZTA; b KAF- 101ZTB; c
KAF- 101ZTC.

Journal of the University of Chemical Technology and Metallurgy, 46, 4, 2011

Fig. 2. Change of the substrate dissolved metal mass, M2: Fig. 3. Change of the samples masses during their phosphating,
a KAF- ZTA; b KAF- ZTB; c KAF- ZTC. M3: a KAF- ZTA; b KAF- ZTB; c KAF- ZTC.

Y. Tumbaleva, D. Ivanova, L. Fachikov

Fig. 4. X-ray gram of the phosphate coating prepared in solution KAF-101ZTA.

Fig. 5. TEM micrographs of phosphate coatings: a KAF- ZTA; b KAF- ZTB; c KAF- ZTC.

irrespective of the P2O5:NO3 ratio, phosphate REFERENCES

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Journal of the University of Chemical Technology and Metallurgy, 46, 4, 2011

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