CHEMICOTHERMAL

METHOD
INPUT

OF

DETERMINING

DURING
Ya.

I.

TREATMENT

AMMONIA

GAS NITRIDING

Matin

UDC 621.785.532.062.5

T h e a m m o n i a input during g a s nitriding is calculated on the b a s i s of e x p e r i m e n t a l data, which in s o m e

c a s e s l e a d s to high gas p r e s s u r e s in the furnace, leakage of a m m o n i a into the shop, which m a k e s for bad
working conditions, i m p r o p e r m e t h o d s of t e s t i n g the furnace, o r an inadequate output f r o m g a s - p r e p a r a t i o n
equipment.
In p r a c t i c e , the gas input is d e t e r m i n e d f r o m a few a v e r a g e d data in the l i t e r a t u r e .
F o r shaft f u r n a c e s with a v o l u m e f r o m 0.007 to 2.8 m 3 it is r e c o m m e n d e d that the a m m o n i a input be
2.1-2.4 m3/h p e r 10 m 2 of s u r f a c e to be t r e a t e d [1].
In Soviet p r a c t i c e the a m m o n i a input is g e n e r a l l y taken as 40 g / k g of p a r t s t r e a t e d .
T h e s e f i g u r e s a r e too g e n e r a l and do not take into account m a n y f a c t o r s t h a t affect the a m m o n i a input.
H o w e v e r , the p r o b l e m of d e t e r m i n i n g the a m m o n i a input for s p e c i f i c conditions m u s t be solved with r e g a r d
to the p a r a m e t e r s of the p r o c e s s and the furnace.
On the b a s i s of n u m e r o u s studies we p r o p o s e a method p e r m i t t i n g calculation of the a m m o n i a input with
a r e l a t i v e l y s m a l l e r r o r (10-12%).
The method was developed on the b a s i s of e x p e r i m e n t a l d e t e r m i n a t i o n s of the a m m o n i a input in the
p r o c e s s of nitriding under v a r i o u s conditions.
The investigation was conducted with c o m m e r c i a l e l e c t r i c f u r n a c e s - shaft, double-wall with a m o v e a b l e
c h a m b e r , and muffle and m u f f l e - f r e e f u r n a c e s of the batch and semicontinuous types.
An a n a l y s i s of the r e s u l t s e s t a b l i s h e d the effect of v a r i o u s technological and furnace p a r a m e t e r s on the
a m m o n i a input.
T h e method developed t a k e s into c o n s i d e r a t i o n the t e m p e r a t u r e , dissociation of a m m o n i a , the duration
of different s t a g e s of nitriding (the p a r a m e t e r s of the p r o c e s s ) , the g e o m e t r i c dimensions of the furnace
c h a m b e r ( e s p e c i a l l y the s u r f a c e of p a r t s in contact with ammonia), and the design and special c h a r a c t e r i s t i c s
of the s y s t e m for sealing the furnace.
The following a s s u m p t i o n s w e r e m a d e in developing the method: 1) the load in the furnace is c l o s e to
nominal; 2) the m e t a l l i c p a r t s of the furnace subject to the influence of the nitriding m e d i u m and the s e a l s
a r e in s a t i s f a c t o r y working condition; 3) a slight and c o n s i s t e n t e x c e s s p r e s s u r e is maintained in the furnace
( e s p e c i a l l y i m p o r t a n t for f u r n a c e s with o r e seals).
The method is b a s e d on:
a) e s t a b l i s h i n g the b a s i c nitriding conditions c h a r a c t e r i z e d by m i n i m a l t e m p e r a t u r e and m i n i m a l d i s sociation of a m m o n i a . The following conditions w e r e taken as basic: t e m p e r a t u r e 500C, dissociation of
a m m o n i a ~ = 15-30%;
b) d e t e r m i n i n g e x p e r i m e n t a l l y for the b a s i c conditions the a v e r a g e g a s input for f u r n a c e s of different
t y p e s and s i z e s with different s y s t e m s of sealing and d e t e r m i n i n g the graphic and analytical r e l a t i o n s h i p s on
this basis;
e) e x p e r i m e n t a l and analytical d e t e r m i n a t i o n of the r e l a t i o n s h i p s and coefficients making it p o s s i b l e to
t a k e changes in nitriding conditions into a c c o u n t - r a i s i n g the nitriding t e m p e r a t u r e and changing the d e g r e e
of d i s s o c i a t i o n of a m m o n i a in r e l a t i o n to the technology.

V. P . Vologdin All-Union S c i e n t i f i c - R e s e a r c h Institute of H i g h - F r e q u e n c y C u r r e n t .

Metallovedenie i T e r m i c h e s k a y a O b r a b o t k a Metallov, No. 3, pp. 5-9, March, 1980.

0026-0673/80/0304- 0161 $07.50 1980 Plenum Publishing C o r p o r a t i o n

Translated from

161

A m m o n i a Input with Operation under Basic Conditions. The furnaces generaUy used for nitriding a r e
batch o r semicontinuous f u r n a c e s of the shaft, double-wall with moveable c h a m b e r , and cupola t y p e s . As exp e r i m e n t s showed, the gas input depends to a c o n s i d e r a b l e extent on the s e a l s - between the muffle and the
c o v e r o r shaft and c o v e r , o r between the muffle and the wall in cupola and double-wall e l e c t r i c f u r n a c e s with
a moveable c h a m b e r .
F o r this r e a s o n , it is expedient to consider two groups of f u r n a c e s s e p a r a t e l y .
The f i r s t group includes f u r n a c e s of r e l a t i v e l y s m a l l size in which the principal seal takes the f o r m of
two flanges with a gasket between them. A w a t e r - c o o l e d r u b b e r g a s k e t is used in shat~ furnaces.
This design p r o v i d e s a good seal with insignificant leakage of the gas, which is t h e r e f o r e neglected in
the calculations.
In furnaces of the second group the main seal is in the f o r m of a c o v e r with filler (chromium ore), and
p a r t of the gas supplied to the furnace is spent on making up the gas that filters through the c o v e r .
The leakage depends mainly on the size of the groove in the c o v e r , the p a r t i c l e size of the ore, the extent to which it is tamped, the p r e s s u r e in the furnace, and also the location of the groove with r e s p e c t to the
cupola.
F o r n o r m a l furnace operation the groove of the c o v e r is -~ 100 x 1000 m m in section and is filled with
o r e with a size of 0.1-2 mm; the e x c e s s gas p r e s s u r e in the furnace is 5-25 m m water column.
The a m m o n i a spent (leakage through the cover) is g r e a t l y affected by the hydrostatic p r e s s u r e of the
~as in the furnace. It is known that the h y d r o s t a t i c p r e s s u r e of the gas r e a c h e s the highest values in the
dome of the furnace [2]. The higher the t e m p e r a t u r e and the g r e a t e r the height of the furnace, the higher the
h y d r o s t a t i c p r e s s u r e . In determining the gas input for basic operation ( t e m p e r a t u r e and dissociation of a m m o n i a taken as constant) it is n e c e s s a r y to take into account only the position of the c o v e r in relation to the
dome of the furnace. In this r e g a r d furnaces with filled c o v e r s can be divided into two groups: a) with a
c o v e r located at the dome of the furnace (with the highest hydrostatic p r e s s u r e at the cover); b) with a c o v e r
located at the bottom of the f u r n a c e (with the lowest hydrostatic p r e s s u r e at the cover).
On this basis, depending on the design and location of the main seal, the method p r o p o s e d (for basic operation) can be used for experimental determination of the gas input for f u r n a c e s of t h r e e groups:
1) f u r n a c e s with a basic seal in the f o r m of two flanges with a c o m p r e s s i b l e gasket between them
(shaft, chamber);
2) f u r n a c e s with a c o v e r at the bottom (double-wall with a moveable c h a m b e r , cupola);
3) f u r n a c e s with a c o v e r at the dome (shaft furnaces).
The gas input Q~ under b a s i c operating conditions was obtained in the c o u r s e of numerous operating
t e s t s of furnaces differing in size.
The gas input in furnaces with a c h a m b e r as l a r g e as 1.5 m 3 sealed by m e a n s of two flanges with a
gasket between them is shown in Fig. 1.
As the size of the furnace is i n c r e a s e d to ~ 1 m 3 the i n c r e m e n t AQ/AV d e c r e a s e s , and the v a r i a t i o n
of Q with V takes the f o r m of a parabola. At l a r g e r furnace sizes the value of AQ/AV r e m a i n s constant and
the v a r i a t i o n of Q with V is linear.
The ammonia input for f u r n a c e s of the f i r s t group can be calculated by the formulas:
for f u r n a c e s with V < 1 m 3
Qg= 2.4 V-- V' + 0.27, .kg/h;
for

(1)

furnaces with V -~ 1 m s

qg= o.3v+ ,.~2, ~

(2)

The gas input for f u r n a c e s of the second and t h i r d groups can be calculated with sufficient a c c u r a c y by
the e m p i r i c a l f o r m u l a (3) [3] that t a k e s into account the c h a r a c t e r i s t i c s of the furnace with a filled c o v e r and
a l s o the dimensions of the furnace c h a m b e r , which a r e v e r y important for l a r g e furnaces, as experiments
have shownz
s~ a

Qg= T-tot.l---o'+ Bi~:.

162

(3)

'

,,oL5

olT I

L_

#,~ ~J

it I

'

=_L_

~75 0,7 o,9

I 3

V,m

Fig, 1, Hourly input of a m m o n i a in furnaces

with a chamber as large as 1.5 m 3 sealed by
means of two flanges with a compressible
gasket between them,
w h e r e P is the p e r i m e t e r of the c o v e r ; s is a value taking into account the r a t i o of the height H to the d i a m e t e r (width) d (the v a r i a t i o n of s with H / d is linear); ~'tot is the t o t a l nitriding t i m e , including the heating,
holding, and cooling t i m e s (Ttot = vii + VB + ~'C); fl is a coefficient accounting for the position of the c o v e r
with r e s p e c t to the height of the f u r n a c e . F o r f u r n a c e s with a low c o v e r (cupola f u r n a c e s and with a m o v e a b l e
c h a m b e r ) /3 = 0.18 k g / m - h , while for shaft f u r n a c e s /~ = 0.25 k g / m - h .
It follows f r o m the data in [4] and our r e s u l t s that with i n c r e a s i n g H / d the a m m o n i a input i n c r e a s e s .
With H / d = 1.5, s = 0.35.
The gas input Q ' g for f u r n a c e s of the second and third groups can be d e t e r m i n e d by m e a n s of g r a p h s
(Fig. 2) or by f o r m u l a s d e s c r i b i n g t h e g r a p h s (see T a b l e 1),
N u m e r o u s t e s t s have shown the good a g r e e m e n t between the t h e o r e t i c a l and e x p e r i m e n t a l values. The
e r r o r in the c a l c u l a t i o n s does not exceed 12%o
A m m o n i a Input during N i t r i d i n g . u n d e r Given Conditions. D e t e r m i n i n g the gas input during operation
under b a s i c conditions m a k e s it p o s s i b l e to c a l c u l a t e the gas input during operation under any given conditions,
i.e., t a k e into account the effect on g a s input of changes in the p a r a m e t e r s of the p r o c e s s - an i n c r e a s e of the
t e m p e r a t u r e and d e g r e e of d i s s o c i a t i o n of a m m o n i a during holding.
If the a m m o n i a input in the p r o c e s s of holding is equal to Qgt p e r h o u r , t h e n p a r t of it - AQ 1 - d i s s o c i a t e s ,
and a constant d e g r e e of d i s s o c i a t i o n is maintained in the furnace:
VN, + H=
VN=+

H=

+ NH=

where VN2+H 2 is the volume of the nitrogen-hydrogen mixture formed in the furnace per hour; VN2+H~.NHs,
total volume of gas passing through the furnace each hour. In conformity with the reaction 2 N H 3 ~ N 2 + 3H2,
the volume of the nitrogen-hydrogen mixture is double the volume of dissociating gas, and therefore
VN,+H , =2A

Qx;

I
ia) 2t

b)

1~

-iJ V, mS,

7V, m

Fig. 2. Hourly input of a m m o n i a in furnaces

with a seal at the bottom (a) and top (b).
163

TABLE 1
Ft~- Volume ]Formula f~x dete~IlaCe ~ , m
c~mf
I~
Q~' ~ / h
group:
!
ScC-

ond

First

0,

IA VS -~"6,8 V - 1

v~<s

I g

4v

v>5

3~V<13

V~13

(4)

0~=o,~25 v+,,~s

(6)

[ ~ - - 0.4
- - "V"s~+3,3V--4
-'~

(6)

(7)

I^,

Og =0,17 V+3,48

v N , + a , + . a , = q~_t,o~ + 2 AQ, = Q~ +A~h;

2A~

as= Ogt-bA~ "

F r o m this one can d e t e r m i n e the volume of gas dissociating in the furnace at t e m p e r a t u r e t 1 (if the
volume of a m m o n i a supplied to the furnace Q g t is known and the d e g r e e of dissociation in the furnace st):
a~

~t

hQl = 2 - - a z "
When the furnace t e m p e r a t u r e is r a i s e d to te at the same value of Qgl, a h i g h e r d e g r e e of dissociation
q2 is established, while the quantity of dissociating gas AQ2 can be d e t e r m i n e d f r o m the e x p r e s s i o n

AQ2----- 2--o~ "

With constant operating conditions (load, t e m p e r a t u r e ) in a furnace of a given type the quantity of a m monia dissociating p e r unit t i m e can be c o n s i d e r e d constant for p r a c t i c a l p u r p o s e s , as experiments have
shown. To maintain the s a m e d e g r e e of dissociation for t e m p e r a t u r e t 1 at a new t e m p e r a t u r e t 2 it is n e c e s s a r y to supply an additional quantity of f r e s h ammonia; the e x c e s s quantity of dissociated ammonia is r e moved in this c a s e .
F o r this p u r p o s e , with holding at t 2 = const, it is n e c e s s a r y , apart f r o m constant supply gas Qgt, to
supply a quantity of ammonia to r e p l a c e the dissociated ammonia in the furnace 2(AQ 2 - AQ1).
Since the r a t i o of the volume of dissociated ammonia to the total volume passing through the furnace
at t 2 is equal to or2, to r e p l a c e the dissociated a m m o n i a (N2 + 3H 2) in a volume 2(2~Q2 - AQ1) of ammonia it
is n e c e s s a r y to p a s s additional a m m o n i a in an amount AQ3, which can be determined with sufficient a c c u r a c y
f r o m the following expression, as experiments have shown:
Qa = (AQ2-- h0x) 2
G2

Then, if the d e g r e e of dissociation r e m a i n s unchanged, the total gas input (Qg2) can be calculated f r o m
the formulas

% = % * LT : - ~ - - 2"v:'z;'~,/ ~ =

~-~

ax
as

2 )
2--as "

Let us take ~2 -- elK2, and then

Qg~=Q~(I -~

2-~

K~

2_2 a,).

(8)

w h e r e K 2 is the r a t i o of the d e g r e e o f dissociation of a m m o n i a in the furnace (with constant a m m o n i a input)

164

at different higher t e m p e r a t u r e s to the d e g r e e of d i s s o c i a t i o n at the m i n i m a l t e m p e r a t u r e .

shown that the value of Kg is independent of the type and size of the furnace.

E x p e r i m e n t s have

To d e t e r m i n e the value of Kg at 500C a constant quantity of a m m o n i a was added to the furnace. When
the c o m p o s i t i o n of the f u r n a c e a t m o s p h e r e stabilized, the d e g r e e of dissociation ~t w a s m e a s u r e d . With no
change in the a m m o n i a input the f u r n a c e t e m p e r a t u r e was r a i s e d 25 . After stabilization of the furnace a t m o s p h e r e at 500, 525, 550, 575, 600, 625, and 650C the d e g r e e of d i s s o c i a t i o n was m e a s u r e d . F r o m t h e s e
e x p e r i m e n t s , which w e r e m a d e with s e v e r a l f u r n a c e s , we plotted the v a r i a t i o n of Kg with t e m p e r a t u r e (Fig.
3). The value of Kg can be d e t e r m i n e d by the following e m p i r i c a l formula:
[ t - - 500~ 2,15

Kg=l+1.1o

lOO /

(9)

w h e r e t and 500 a r e the c u r r e n t and b a s i c operating t e m p e r a t u r e s , r e s p e c t i v e l y .

F o r m u l a (8) m a k e s it p o s s i b l e to c a l c u l a t e the gas input f o r v a r i o u s f u r n a c e s in the r a n g e of nitriding
t e m p e r a t u r e s on condition that the d i s s o c i a t i o n of a m m o n i a r e m a i n the s a m e as under b a s i c operating conditions. H o w e v e r , with a change in t e m p e r a t u r e the p r o c e s s changes and also the d e g r e e of d i s s o c i a t i o n of atom oni a.
At any temperature t2 a given degree of dissociation ~G mustbe maintained so that ~I < ~G < ~2, and
apart from the basic quantity of ammonia Qgl it is necessary to supply ammonia in a volume of ~Q4 so as to
replace the quantity of dissociated ammonia formed in the furnace. Letus assume ~G = sin (n indicates how
many times the dissociation of ammonia under the given conditions exceeds the dissociation under basic operating conditions). Since a quantity of ammonia AQ2 dissociates hourly in the furnace at temperature t2 and
degree of dissociation ~2 is established, the excess amount of dissociated ammonia that must be removed
from the furnace each hour can be taken as equal to 2(AQ2 -- nAQi), and the additional quantity of ammonia
AQ4 that must be added to the furnace

A Q, -

(aQ2--n AQ,) 2
rt,~

The hourly gas input QgB during holding for any operating conditions can be calculated by the equation

=%

- -

2.,

(10)

T h i s equation holds t r u e for any operating conditions in the furnace and m a k e s it p o s s i b l e to s e l e c t

v a r i o u s b a s i c o p e r a t i n g conditions. F o r our b a s i c operating conditions (t = 500C, ~ = 15-30%)
Qgl -----Qg and
%s =

' + 2-

Kg
5
4

2
1
Y80

525

.~SD

575

6DD

62Y

Fig. 3. V a r i a t i o n of Kg with furnace

temperature.

165

The total gas input for the entire cycle

Qgt~ = 0~H~n+Qg~B+ Qgc~c'

where Qgtot is the total gas input for the entire nitriding cycle; QgR, QgB, and QgC, hourly gas inputs in
the process of heating, holding, and cooling; vii, ~'B, and TC, heating, holding at t = const, and cooling
times, respectively.
To simplify the calculations and reduce the e r r o r , as the experimental data show, one can use QgH
and QgC f o r all basic operating conditions, i.e.,
QgH-QgC= Qg;
then

(12)
In selecting the size of piping used for the exhaust gases it is n e c e s s a r y to base the calculations on the
gas input at the highest t e m per a t ur e (in the holding period with t -- const), taking into account the l ar g e r volume of exhaust gases due to dissociation of ammonia to a given value c~. Inthis case the input is determined
from the expression

Q= (! + aG) QgeComparison of the experimental and theoretical data indicates good agreement.

CONCLUSIONS
1. The method given has been verified experimentally with commercial furnaces. It is possible to calculate the ammonia input during gas nitriding, taking into accountthe parameters of the furnace and the process.
2. The method per m i t s technical control of the gas preparation and supply equipment, standardization
of the equipment, and reduces the input of ammonia and pollution of the shop atmosphere.

LITERATURE CITED
i.
2.
3.
4.

166

Efco-RoyceFurnace Ltd., Nitriding (1968).

V.E. Grum-Grzhimailo, Flame Furnaces [in Russian], Parts I, If, Gosmashmetizdat,MoscowLeningrad (1932).
Ya. I. Matin, eAmmoniainput during gas nitriding," im Electroteehnical Industry, Electrothermy Series
[in Russian], No. 100, Inform~lektro, Moscow (1970), p. 4.
Yu. Tel'nyuk and B. Kalmykov,Eliminationof Nonproductive Ammoniaduring Nitriding [in Russian],
TsBTI, Mossovnarkhoz (1966).