M e t a l Science a n d Heat Treatment Vol. 38, Nos.

I - 2, 1996

U D C 621.78.08

ANALYSIS OF POLYMER-BASED QUENCHING MEDIA

A. V. Sverdlin,l G. E. Torten,~ and G. M. Webster I

Translated from Metallovedenie i Termicheskaya Obrabotka Metallov, No. 2, pp. 9 - 12, February, 1996.

The characteristics of quenching liquids such as oils and salt and polymer solutions c a n change during use
because of impurities, degradation, or other causes. In this connection, desirable results in quenching are
obtained by periodic control of the composition and properties of the quenching medium. The method for
analyzing oils is quite developed, whereas no similar method for analyzing quenching media based on
water-soluble polymers exists, although they are becoming widely used in industry. The article concerns the
properties of aqueous solutions of polymers and methods for their determination.

Let us consider general analytical methods used at pre-
sent for investigating the properties o f quenching liquids
based on polymers.
Refractive index. The most general and inexpensive
method for analyzing polymer-based liquids consists in
evaluating the refractive index ( n o ) measured at the sodium
wavelength D = 589.3 nrn. The refractive index depends on
the temperature of the solution. Therefore, it should be fixed
in evaluating n o .
It should be noted that the refractive index characterizes
not only the properties of the polymer or its concentration in
water, but also the presence of inclusions like oils or salts
(Fig. 1). Any worsening of the parameters of the polymer so-
lution, for example, its oxidizability, also causes a change in
n o . Since the refractive index of the solution depends on the
contamination of polymer solutions exert a minimum effect
on the quenching medium (see Fig. 2b ).
Viscosity can be measured by various methods. The most
popular is the method of capillary viscometry. In this case the
viscosity is determined by the formula
rI = Ts/Tw,
where xs and Xw are the times taken by flows of the aqueous
solution of the polymer and the solvent to cover a specified
distance in the tube.
.o /

concentration of the components, the sensitivity of the sug- 1.346 /

gested method decreases with a decrease in the concentration
of the substances dissolved in the cooling medium. This ex-
1.341
/
plains why the refractive index is inapplicable for analyzing
quenching liquids with low polymer concentrations, such as
1.336
/
sodium polyacrylate. Thus, estimation of the state of a cool-
ing liquid from the refractive index is a comparatively simple
method used in heat treatment shops. However, its limited
/
5 I0 t5 Cp, %
sensitivity requires that the other parameters of the cooling
medium also be evaluated periodically.

/
nD
Viscosity. Viscosity (rl) or the resistance to the motion of
13515
the flow of a quenching liquid based on a water-soluble poly-
mer is a function of the molecular size. Therefore, when the
/
size of a molecule of a linear polymer and hence the molecu-
lar weight are increased, the viscosity is increased too (Fig.
2a). Since the viscosity depends on the temperature (Fig. 3),
1.3495

13475 J
/
this characteristic of polymer solutions should be compared
at the same temperature. It is interesting that low levels of salt /, I 2 3
I
5 C,,%

Bradley University, Peoria, Illinois; Fig. I. Dependence of the rcfractivc index n D on the polymer concentration
Union Carbide, Tarrylown, New York. Cp (a) and the salt (sodium nitrate) concentration C s (b) in a cooling liquid.

56
0026--0673,'9610102-0056515C~1996 Plenum PublishingCorporation
Analysis of Polymer-Based Quenching Media 57

q 103, cSt q, St

3011 5.! ~,

/ ,.o/ . /
IOO 4.9

" 0 2 4 C,, % Beginning

Fig. 2. Dependence o f the viscosity q of the cooling liquid on the molecular

weight I.t o f the polymer (a) and the concentration of salt (sodium nitrate) C s
in it at 38C ( b )
\ ) ~ End

q x 103, cSt
3OO

,,o ///
,///i Fig. 4. Cannon - Fenske tube for determining the viscosity q (the arrows in-
dicate the beginning and the end of the measured region).

38C
,0o /(I/ / It should be noted that viscometry is sensitive to low
polymer concentrations in the solution, and therefore this
8o / / / / method can be widely used for estimating the state of quench-
//// ing aqueous solutions with a low concentration of high-mo-
oo /Z/t" lecular-weight polymers such as sodium polyacrylate.
Gel-penetrating chromatography (GPC). Organic sub-
stances that form a polymer quenching liquid become de-
graded during use, i.e., lose their initial characteristics. The
most promising method for determining the degree of clcgra-
dation of a polymer in a solution is gel-penetrating chroma-
30 tography. This method is used only in special cases because it
5 15 25 35 45 Cp, %
is comparatively expensive. However, it makes it possible to
Fig. 3. Viscosity rI as a function of the polymer concentration (Cp) in a estimate the state of the polymer quite completely. Any dis-
quenching medium at different temperatures (the numbers at the curves). cussion of the properties of a polymer is unthinkable without
using this method.
GPC is conducted by injecting a small amount of the
polymer liquid into an apparatus with a microporous cross-
The most popular device for measuring viscosity is a linked polymer. The porosity of the apparatus is sufficiently
Cannon - Fenske glass capillary tube (Fig. 4), which has two low for fractionation of the polymer molecules. This occurs
marks fixing a specified distance. Each tube is characterized due to the "exclusivity of the charge." Indeed, exclusive-
by a coefficient C used in calculating the viscosity of the in- charge chromatography is a more modem method. A solvent
vestigated liquid. The viscosity q (in cSt) is determined by such as water or chloroform circulates continuously through
the formula the apparatus under pressure until different polymer frag-
ments are extracted. The process makes it possible to conduct
rl = C x , a molecular analysis of the distribution of the "mean" mo-
lecular size in the polymer. Coarse molecular fragments of
where x is the time taken by the liquid to pass the distance the polymer are removed from the apparatus in the first'turn,
between the two marks. because they cannot pass through the micropores quickly.
The viscosity of a cooling liquid is affected by the poly- A typical fractionation chromatogram is presented in
mer concentration in the aqueous solution (Fig. 3). The meas- Fig. 5. One way to use chromatograms consists in calculating
urement of :viscosity can be used for controlling the concen- the area S~h of the shift between the fresh and used polymer
tration of the quenching aqueous solution. (Fig. 6). If the same amount of polymer has been injected and
58
! I I I I !
Is
Fig. 5. Chromatogram of polymer fractionation (I s is the intensity of the sig-
nal, xc is the confinement time): / ) a high-molecular-weight compound; 2 )
a low-molecular-weight compound.
removed, the area below the curves is the same. If the poly-
mer has become degraded, the chromatogram will have a
more smeared peak. This smeared (widened) peak forms due
to the larger amount of fine molecules appearing in the degra-
dation of the initial, coarser molecules. Thus, a greater area of
the peak shift will indicate a higher degradation. It should be
noted that the comparative analysis should be conducted for
"normalized" chromatograms where the total area of both
curves is the same. Only in this case will we determine the
true "shift area." GPC analysis is expensive and is sometimes
inexpeditious for small heat treatment enterprises. However,
it can be ordered from the supplier. In many cases the supplier
of polymer quenching media will serve the customer free of
charge.
We have shown above that the refractive index is sensi-
tive to different sources of contamination and rather insensi-
tive to the molecular size or weight of the polymer quenching
TABLE 1
Concentration of Vc~l x Vcool at 343C
sodium nitrate, %
deg/sec
0 39.0 25.3
3 54 0 31.8
6 65.8 350
Water* 61.8 33.0
Note. The data were obtained by analyzing the cool-
ing curves of a specimen 50 x 100 mm in size of cor-
rosion-resistant steel 304 with a thermocouple fused at
its center in a 20% aqueous solution of Yukon A
polymer contaminated with sodium nitrite salts
* A cooling medium that contains no polymer or im-
purity (distillate).
A . V . Sverdlin et al.
Fig. 6. Chromatogram of a fresh
( I ) and a used (2) polymer solution
(Is is the signal intensity, xc is the
D Tc confinement time).
liquid. On the other hand, the viscosity is more sensitive to
the polymer size and less sensitive to its contamination. In
this connection, a parameter A is introduced to describe the
relation between the concentrations determined from the re-
fractive index (C,,o) and the viscosity (C,1) [1]:
A = Cno - C n ,
We investigated the variation of the parameter A of a
polymer solution during use in a quenching tank. Then we es-
tablished the causes of the marked changes in A.
Unfortunately, the very concept of A is now presented
differently from the initial interpretation. Currently, the pa-
rameter A is said to be an indicator of the stability of the poly-
mer quenching liquid. Below we present data on A and the
area shift S~h in a chromatographic analysis:
A Ssh
I.I . . . . . . . . . . . . . . . . . . . . . 7
3.6 . . . . . . . . . . . . . . . . . . . . . 35
3.1 . . . . . . . . . . . . . . . . . . . . . 67
0.5 . . . . . . . . . . . . . . . . . . . . . 27
1.6 . . . . . . . . . . . . . . . . . . . . . 47
0 ...................... 7
It can be seen that the parameter A is not correlated with
the area shift in GPC.
The degree of variation of A depends on the type and
level of contamination, as well as on the stability of polymer.
For this reason, we cannot state that an increase in A is an
indicator of the polymer stability. At the same time, A can be
a kind of qualitative parameter of the stability of a polymer
quenching liquid.
T h e r m a l conductivity. In many cases heat treatment is
accompanied by contamination of the tank with the quench-
ing liquid by various salts. For example, this may happen in
quenching aluminum alloys, if they are heated in a salt solu-
tion. Contamination of polymer quenching liquids can influ-
Analysis of Polymer-Based Quenching Media
ence the cooling rate (see Table I), and therefore it is impor-
tant to analyze and evaluate the amount of salts present in
them. A simple and inexpensive method for determining con-
tamination with salts consist in evaluating the thermal con-
ductivity of the solution. In practice we can obtain a linear
dependence of the thermal conductivity of the solution on the
number density of salt ions in the quenching liquid in the ab-
sence of contamination [2]. At the same time, the determina-
tion of the thermal conductivity can be used for controlling
the amount of salt impurities, because an increase in the ther-
mal conductivity indicates the presence of a salt in the
solution.
59
CONCLUSION
The quality of quenching in polymer solutions can be im-
proved substantially by periodic control of the state of the
quenching medium. The controlled parameters can be the re-
fractive index, viscosity, and thermal conductivity of the so-
lution, and in some cases it is expeditious to resort to gel-
penetrating chromatography.
REFERENCES
I. E. R. Miller, Heat Treatment, No. 15, 24 - 27 (1983).
2. A. 1. Vogel, A Textbook on Quantitative Inorganic Analysis, In-
cluding Elementary Instrumental Analysis, Wiley, New York
(1968).