56

F I Z I K A GORENIYA I VZRYVA

STUDY O F THE CONDITIONS O F U T I L I Z A T I O N OF H E A T - R E S I S T A N T E X PLOSIVE NO. 2 AT E L E V A T E D T E M P E R A T U R E S

A. G. Strunina, V, G. Abramov, S. A. Lovlya, and V. A. Dement'ev Fizika Goreniya i Vzryva, Vol. 2, No, 2, pp. 90-95, 1966 U D C 541.427.6
I n c r e a s e s in the depth of oil and gas w e l l s have led to c h a n g e s in d r i l l i n g and o p e r a t i n g c o n d i t i o n s . F o r t h e e q u i p m e n t e m p l o y e d in t r o u b l e - s h o o t i n g and p r o duction o p e r a t i o n s i n v o l v i n g the u s e of e x p l o s i v e s [1] the i n c r e a s e in the t e m p e r a t u r e and p r e s s u r e at the w o r k i n g l e v e l is of d e c i s i v e s i g n i f i c a n c e . T h e high h y d r o s t a t i c p r e s s u r e m a k e s it n e c e s s a r y to i n c r e a s e the weight of the c h a r g e to c o m p e n s a t e for the r e duced e f f e c t i v e n e s s of the e x p l o s i o n u n d e r t h e s e cond i t i o n s . The t e m p e r a t u r e and p r e s s u r e , by d e t e r m i n i n g the r a t e of t h e r m a l d e c o m p o s i t i o n and h e n c e the l i m i t s of a u t o - i g n i t i o n , r e s t r i c t the r e g i o n of a p p l i c a t i o n of e x p l o s i v e s , s i n c e an a r b i t r a r y e x p l o s i o n b e f o r e the c h a r g e h a s r e a c h e d the p r e s c r i b e d level, u s u a l l y with s e r i o u s c o n s e q u e n c e s f o r the well, i s o b v i o u s l y i n t o l e r a b l e . Table I E x p e r i m e n t a l v a l u e s of C r i t i c a l Autoignition D i a m e t e r s and Induction Periods
T~, C d,, C1T~ t,, ]3I

S p e c i a l e m p h a s i s was p l a c e d on the c h a r a c t e r i s t i c s of the p r o c e s s ttm.t a r e i m p o r t a n t in p r a c t i c a l a p p l i c a tions. T h e r m a l a u t o - i g n i t i o n o c c u r s when the h e a t f the d e c o m p o s i t i o n r e a c t i o n cannot e s c a p e f r o m the c h a r g e , thus c a u s i n g a c c e l e r a t i o n of the r e a c t i o n and s e l f h e a t i n g . T h e t h e o r y is b a s e d on an e x a m i n a t i o n of the r e l a t i o n b e t w e e n the h e a t r e l e a s e due to the c h e m i c a l r e a c t i o n and h e a t r e m o v a l [2]. The p r o b l e m r e d u c e s to the j o i n t solution of the s y s t e m of equations of c h e m i c a l k i n e t t e s and h e a t t r a n s f e r and d e s c r i b e s the s p a c e and t i m e d i s t r i b u t i o n of t e m p e r a t u r e s and r e a c t i o n r a t e s . T h e t h e o r y i n v o l v e s c o n s i d e r a t i o n of: 1) the c r i t i c a l c o n d i t i o n - - t h e r e l a t i o n b e t w e e n the s y s t e m p a r a m e t e r s (ambient t e m p e r a t u r e To, c h a r g e d i a m e t e r d, conditions of h e a t t r a n s f e r b e t w e e n the c h a r g e and the a m b i e n t m e d i u m ) c h a r a c t e r i z i n g t r a n sition f r o m s m o o t h b u r n u p of all the m a t e r i a l with a low l e v e l of heating to an e s s e n t i a l l y n o n s t a t i o n a r y (with ignition) r e a c t i o n . T h e c r i t i c a l condition of t h e r m a l e x p l o s i o n can be w r i t t e n in the f o r m d~, = a ~ (Bi) ro ~ exp

(E/RTo),

177 I5S
t71

~.6 3

58:2 88,9 258,5

w h e r e a is a p a r a m e t e r c h a r a c t e r i z i n g the t h e r m o p h y s i c a l p r o p e r t i e s of t h e m a t e r i a l ; (m) =

What a r e the p r e s s u r e s and the t e m p e r a t u r e s now b e i n g o r l i k e l y to be e n c o u n t e r e d by oil w o r k e r s , the c h i e f u s e r s of h e a t - r e s i s t a n t e x p l o s i v e s ? A b r o a d , w e l l s have been d r i l l e d to about 8000 m, in the Soviet Union to 6000 m . T h e c o r r e s p o n d i n g t e m p e r a t u r e s a r e 240 and 220 ~ C, the c o r r e s p o n d i n g p r e s s u r e s 1 3 0 0 - 1 0 0 0 k g f / c m ~. If we s t a r t f r o m m a x i m u m g e o t h e r m a l g r a d i e n t s , then at d e p t h s of the o r d e r of 7000 m it is p o s s i b l e to a n t i c i p a t e t e m p e r a t u r e s c l o s e to 350" C, p r o b a b l y a t the l i m i t of ~he r a n g e of p r a c t i c a l u t i l i z a t i o n of e x p l o s i v e s . In view of the g e n e r a l t r e n d t o w a r d an i n c r e a s e in d r i l l i n g depths, the i n c r e a s e in the n u m b e r of h i g h - t e m p e r a t u r e w e l l s (at l e a s t 1 3 0 - 1 8 0 ~ C), the d e v e l o p m e n t of g e o t h e r m a l h e a t s o u r c e s , and the e x i s t e n c e of o t h e r a r e a s of a p p l i c a t i o n of h e a t - r e s i s t a n t e x p l o s i v e s , the e s t a b l i s h m e n t of c o r r e c t c o n d i t i o n s of u t i l i z a t i o n is a p r o b l e m of g r e a t i m p o r t a n c e . Our a i m was to i n v e s t i g a t e the c h a r a c t e r i s t i c s of t h e r m a l e x p l o s i o n and d e t e r m i n e the e x p l o s i v e p r o p e r t i e s of c h a r g e s of h e a t - r e s i s t a n t e x p l o s i v e No. 2 (conventional d e s i g n a t i o n ) a t c o n t r o l l e d t e m p e r a t u r e s .

m 2

[ ) / m ; + 4 - Bl]exp

d~+4-m-2
Bl

is a function r e p r e s e n t i n g the d e p e n d e n c e of the c r i t i c a l condition on h e a t t r a n s f e r between the s p e c i m e n and the a m b i e n t m e d i u m [3, 47; the Blot n u m b e r Bi = c~d/2~ c h a r a c t e r i z e s the h e a t t r a n s f e r c o n d i tions ; c~ i s the c o e f f i c i e n t of h e a t t r a n s f e r f r o m the s p e c i m e n s u r f a c e to the a m b i e n t m e d i u m ; d, d . a r e the d i a m e t e r of t h e s p e c i m e n and its c r i t i c a l v a l u e ; k is the h e a t c o n d u c t i v i t y of the s p e c i m e n . 2. The a u t o - i g n i t i o n induction p e r i o d tin d. The c r i t i c a l value of the induction p e r i o d t , is r e l a t e d with the t e m p e r a t u r e To by the e x p r e s s i o n t , = = b exp (E/RT0), above the l i m i t tin d = t . f { d / d . ) [5], w h e r e b i s a p a r a m e t e r c h a r a c t e r i z i n g the p r o p e r t i e s of the m a t e r i a l . 3. T h e depth of p r e - e x p l o s i o n d e c o m p o s i t i o n ~7+ (depth of r e a c t i o n d u r i n g the induction period}. T h e q u a n t i t y 7+ is b a s i c a l l y d e t e r m i n e d by the k i n e t i c p r o p e r t i e s of the s y s t e m i n v e s t i g a t e d . Thus, for n o n a u t o c a t a l y t t c r e a c t i o n s ~+ is s m a l l ( s e v e r a I

COMBUSTION,

EXPLOSION,

AND

SHOCK WAVES the acid decomposition products, may stabilize the process. The pressure, on the other hand, may undoubtedly reduce the critical temperature if the gaseous decomposition products have a catalytic action on the p r o c e s s . It-to ~ _

57

p e r c e n t ) , for a u t o e a t a l y t i e r e a c t i o n s ~?+ m a y r e a c h large values. T h e c h a r a c t e r i s t i c s c o n s i d e r e d above make it p o s s i b l e to s e l e c t the conditions of u t i l i z a t i o n of an e x p l o s i v e at e l e v a t e d t e m p e r a t u r e s . T h e e x p e r i m e n t s w e r e set up as follows. T h e test c h a r g e was placed in a t e m p e r a t u r e - c o n t r o l l e d r e a c t i o n v e s s e l . Between the s u r f a c e of the s p e c i m e n and the wall we left a c l e a r a n c e 0.1 d wide filled with sand to p e r m i t the e s c a p e of the g a s e o u s d e c o m p o s i t i o n p r o d u c t s . The h e a t i n g of the s y s t e m was m e a s u r e d with a t h e r m o c o u p l e and r e c o r d e d with a E P P - 0 9 p o t e n t i o m e t e r . The effective heat t r a n s f e r coefficient c~ was d e t e r m i n e d in each v e s s e l by the r e g u l a r r e gime method [6]. The Blot n u m b e r was kept equal to about 5~ The t i m e f r o m the point at which heat t r a n s f e r agent at t e m p e r a t u r e To was f i r s t supplied to the j a c k e t of the v e s s e l to the point at which the c e n t e r of the c h a r g e r e a c h e d the t e m p e r a t u r e T0 was taken as the p r e l i m i n a r y h e a t i n g t i m e . The induction p e r i o d was r e c k o n e d f r o m p r e l i m i n a r y h e a t i n g t i m e . As the c r i t i c a l a u t o - i g n i t i o n t e m p e r a t u r e i T , ) we took the m e a n of the m a x i m u m t e m p e r a t u r e (Ta) c o r r e s p o n d i n g to s m o o t h d e c o m p o s i t i o n of the s y s t e m and the the m i n i m u m t e m p e r a t u r e (Ty) at which ignition takes place, and as the c r i t i c a l induction p e r i o d (t,) the m e a n of the induction p e r i o d at T = T 2 and the t i m e r e q u i r e d to a c h i e v e m a h e a t i n g of the s y s t e m a r T = T 1. Of c o u r s e , the eondition~ e x a m i n e d above a r e not the s a m e a s those in w e l l s , The chief d i f f e r e n c e is that in a well the explosive is in contact with the liquid f i l l i n g the b e r e h o l e , which, a s a r u l e is u n d e r high h y d r o s t a t i c p r e s s u r e . SinCe the c o m p o n e n t s of the liquid (chiefly mud) vary f r o m weli to well and s o m e t i m e s even in the s a m e well, it is i m p o s s i b l e to find a u n i v e r s a l m e d i u m to r e p r e s e n t the solution.

Fig. 2. T e m p e r a t u r e t i m e c u r v e . In d e t e r m i n i n g the c r i t i c a l t e m p e r a t u r e s we u s e d c h a r g e s 1.6, 2.0, and 3.0 em in d i a m e t e r (Table 1). At l a r g e d i a m e t e r s this p a r a m e t e r was not d e t e r m i n e d owing to the length of the induction periods, which r e a c h e d h u n d r e d s of h o u r s . The data of T a b l e 1 a r e well d e s c r i b e d by the equations

30600
d 2~-, 1 6 - lO-2~ Rr0 em, (1)
30800

t , = 7.2 9 10-~4e rohr.

(2)

Ia o r d e r to u s e equation (1) u n d e r d i f f e r e n t heat t r a n s f e r conditions it is c o n v e n i e n t to w r i t e it in the form

~0600

d 2, = 2.2 9 10-~~ (B]) T~oe reT~ hr.

(3)

t~ ~,0-
/X

rind

02c]r
eS Z~5 o6

E x p r e s s i o n (2) is not affected by changes in Bi [7]. In i n v e s t i g a t i n g the laws of v a r i a t i o n of the i n d u c tion p e r i o d in the r e g i o n of s u p e r c r i t i c a l t e m p e r a t u r e s we used c h a r g e s with d i a m e t e r s of 1.6, 2, 3, 4.2, 5, 8.4 cm. Most of t h e s e m e a s u r e m e n t s w e r e made at t e m p e r a t u r e s not exceeding 1 8 5 - 1 8 7 ~ (Table 2)~ Using the data of T a b l e 2, in Fig. 1 we have plotted the r e l a t i o n between induction period and c h a r g e d i a m e t e r , which is well d e s c r i b e d b y the f o r m u l a
t / t , = 4.5 e - "~ (dra,)

(4)

>

Fig. io ]:nduction p e r i o d a s a function of t e m p e r a t u r e and c h a r g e diameter, i) d = 8.~ era; 2 / d = 5 c m ; 3) d = 4.2 era; 4) d = 3 era; 5) d = = 2 e r a ; 6 ) d = 1.6 era. However, all s o l u t i o n s give an a k a l i n e r e a c t i o n and it m a y be a s s u m e d that in i t s e l f contact between the e x p l o s i v e and the s o l u t i o n will not s e r i o u s l y affect its heat r e s i s t a n c e , and, in fact, by n e u t r a l i z i n g

The t i m e - t e m p e r a t u r e c u r v e s a r e p r e s e n t e d in Fig. 2. T h e i r form i n d i c a t e s that the t h e r m a l d e c o m p o s i t i o n of s y s t e m No. 2 is a s e l f - a c c e l e r a t i n g p r o c e s s c h a r a c t e r i z e d b y l a r g e induction p e r i o d s and r e a c t i o n depths at ignition. In the r e g i o n of c r i t i c a l t e m p e r a t u r e s t h e r e a r e two m a x i m a on the t e m p e r a t u r e - t i m e c u r v e . As a r u l e , all the s p e c i m e n s b u r n e d smooflfly, and the r e a c t i o n v e s s e l r e m a i n e d i n t a c t . Only in the experiment with a charge 8.4 em in diameter was a t r a n s i t i o n from c o m b u s i o n to d e t o n a t i o n and f r a c t u r e of the v e s s e l o b s e r v e d . However, s i n c e the e x p e r i m e n t s were conducted u n d e r conditions of f r e e e s c a p e of gas, it cannot be a s s u m e d that in a well the t h e r m a l a u t o - i g n i t i o n of s m a l l torpedo c h a r g e s will be confined to smooth c o m b u s t i o n .

58

F I Z l K A GORENIYA I VZRYVA

Tabte 2

T e m p e r a t u r e Dependence of Induction P e r i o d at D i f f e r e n t C h a r g e D i a m e t e r s (Si = 5.5)

d, c m 8.4 To, c*C 175

ti~d,bX
1.4

rind
t.

9 --

d,

- d, c m To,~

tindhr

tind
t~ JJ

5.0

154 157 160 164 166 170 173 176 180 152 156 162 166 170 175 176 178 182

259.0 177,0 114,6 54,0 48.6 21,6 12,3 4:5 1.5 352.0 240.0 101.2 68,2 !9.2

0.72 0.62 0,51 0.34 0,3t 0.22 0,17 0,07 0,03 0,78 0.75 0.52 0.49 0.29 0.23 0.12 0.07 0.03

2.04 2,38 2.80 2.95 3,57

1.31 1.66 1.90

1,49

3.0

160 165 170 180

172 176 180 185 189 190 195

206.0 121.0 60.3 12.6 82.0 47.5 25.6 13,3 3.5 0.2

0.97 0,85 0,60 0,28

1.00
1.21 1,42 2 14 1,06 1,22 2,00 2,04 2.88

2.0

0,98 1.15 1.71 2.00 2,44 2.48 2.76 8.23

1,47
1.6

1.75

0.78 0.52 0.41 0.27 0.09 0.02

1.00

1.43 1.74

4.2

4.6

7.2 3.9 1.2

178 180 185 I90 195

52.5 40.0 15.3 6.0 0.6

0.88 0.66 0.29 0,04

0.99

1.05 1.14 t .54 1,90

1.63

COMBUSTION,

EXPLOSION, AND SHOCK WAVES

59

F r o m (2)-(4) u n d e r the given heat t r a n s f e r condit i o n s we can c a l c u l a t e the t i m e r e q u i r e d b y a s p e c i m e n of given d i a m e t e r at L e m p e r a t u r e T O (ambient t e m p e r a t u r e ) to ignite s p o n t a n e o u s l y . With this aim, for a s e l e c t e d t e m p e r a t u r e T Owe d e t e r m i n e d the c r i t i c a l d i a m e t e r s (d,) and i n d u c t i o n period (t,) f r o m (2) and (3), and t f r o m (4). In a c c o r d a n c e with the s c h e m e p r o p o s e d we e s t i m a t e d the u p p e r safe t e m p e r a t n r e limit, which we took as the t e m p e r a t u r e a t which the s p e c i m e n failed to ignite a f t e r 6 h r . The c a l c u l a t i o n s w e r e p e r f o r m e d for an e x p e r i m e n t a l value of Bi = = 5.5. * The r e s u l t s of the c a l c u l a t i o n and the e x p e r i m e n t a l data a r e presented in T a b l e 3. U s i n g Eqs. (2)-(4), in p a r t i c u l a r , we can e s t i m a t e the r e d u c t i o n in heat r e s i s t a n c e of a c h a r g e with i n c r e a s e in its d i a m e t e r , which in a n u m b e r of c a s e s is v e r y s u b s t a n t i a l . N a t u r a l l y , when w o r k i n g in wells this u p p e r t e m p e r a t u r e l i m i t will be r e d u c e d by taking into a c c o u n t the p o s s i b l e n e g a t i v e effect on the p r o c e s s of high p r e s s u r e and contact between the explosive and the liquid, as weI1 a s by the need to i n t r o d u c e c o r r e c t i o n s f o r the i n a c c u r a t e d e t e r m i n a t i o n of the t r u e t e m p e r a t u r e tn the b o r e h o l e . U n d e r d e e p - w e l t c o n d i t i o n s with a v i s c o u s mud the l o w e r i n g of the torpedo m a y be a slow p r o c e s s , so that the h e a t i n g t i m e m a y be prolonged, and s o m e t i m e s , when t h e r e a r e c o m p l i c a t i o n s , the charge m a y be stuck for long p e r i o d s in the h i g h - t e m p e r a t u r e zone. T h e r e is a l s o a p o s s i b i l i t y of defective t o r pedoes b e i n g b r o u g h t back to the s u r f a c e . A c c o r d i n g l y , it is u s e f u l to know how the b e h a v i o r of e x p l o s i v e s is affected by the d u r a t i o n of h e a t i n g and to what extent this f a c t o r affects the safety of b r i n g i n g a defective t o r p e d o back to the s u r f a c e . E x p e r i m e n t s w e r e p e r f o r m e d to d e t e r m i n e the r e l a t i v e efficiency, d e t o nation velocity, and i m p a c t s e n s i t i v i t y of s p e c i m e n s held f o r d i f f e r e n t t i m e s at c o n s t a n t t e m p e r a t u r e (Fig. 3). T h e e f f i c i e n c y was m e a s u r e d from the e x p a n s i o n of the cavity of a lead bomb fo!lowing an e x p l o s i o n , the change in weight was d e t e r m i n e d by weighing the c h a r g e s b e f o r e and a f t e r heat t r e a t m e n t . Table 3 C a l c u l a t e d and E x p e r i m e n t a l V a l u e s of the U p p e r Safe T e m p e r a t u r e Limit
~, ~ d, CFfl Expt. 1,6 2,0 3.0 4.2 5,0 6.5 8.4 190 187 176.5 I75 Calc. 190.5 187.0 180.5 174_5 171.0 168.5 162.0

The expansion of the cavity following explosion of the untreated charge and the weight of the latter were taken as unity. For comparison, the same figure depicts the relation between the relative efficiency and the a m o u n t of i n e r t additive (tale) r e p l a c i n g part of the e x p l o s i v e . It follows f r o m the e x p e r i m e n t s that even a f t e r quite p r o t r a c t e d t r e a t m e n t ( t / t i n d 0.7} the c h a r g e r e t a i n s s a t i s f a c t o r y efficiency and that t h e r m a l d e c o m p o s i t i o n is a c c o m p a n i e d by the f o r m a t i o n of volatile products that a r e r e m o v e d f r o m the charge. The d e c r e a s e in efficiency of c h a r g e s of the s a m e s i z e is a c c o m p a n i e d by a m a r k e d d e c r e a s e in d e t o n a tion velocity. F o r r / r i n c l ~ 0.7 the detonation velocity d e c r e a s e s by about 10%.

0.6
0 0.2 04 0.6 0.8

talc ,Z t/lind

Fig. 3. Relative efficiency (I) and relative weight (2) as functions of the duration of heat treatment. The straight line (3) represents the change in relative efficiency with increase in inert additive. The impact sensitivity of the treated charges was tested on an impact testing machine under standard conditions. It was found that after treatment (at t/tind 0.8) the i m p a c t s e n s i t i v i t y i n c r e a s e s to 80-95~c f r o m a s t a r t i n g value of about 50%. In o r d e r to i m p r o v e the p o s s i b i l i t y of the r e p e a t u s e of torpedoes with c h a r g e s composed of s y s t e m No. 2 we set up e x p e r i m e n t s with a r t i f i c i a l i n t e r r u p t i o n of the heat t r e a t m e n t (after a c e r t a i n p e r i o d of t i m e t 1 < lind). The e x p e r i m e n t s w e r e p e r f o r m e d on c h a r g e s with d = 42 m m at t e m p e r a t u r e s of 180 and 175 ~ C and different t i m e s t:, It was found that s y s t e m No. 2 has a " m e m o r y effect, ~ i. e . , when heat t r e a t m e n t is r e p e a t e d the t i m e r e q u i r e d for a u t o - i g n i t i o n is t2 = tind - t~ where tin d is the induction p e r i o d at that t e m p e r a t u r e d e t e r m i n e d from e x p r e s sion (4). T h e r e f o r e the r e p e a t use of a torpedo will be c o m p l i c a t e d by an i n c r e a s e in the r i s k of r e c o v e r ing it, a d e c r e a s e in efficiency, and a s h o r t e n i n g of the t i m e d u r i n g which the torpedo can s a f e l y be left in the well. SUMMARY I. Equations for c a l c u l a t i n g the temperatures at which it is safe to use charges of system NOo 2 have been obtained under specified experimental conditions, together with formulas for calculating the induction periods of charges of system No. 2 at any temperatures. 2~ Preliminary experiments have shown that the explosive system investigated has a "memory effect." 3o It has been found that with increase in the time spent by the charges in the well their explosive ca-

*In p r a c t i c e Bi is m u c h g r e a t e r , but when Bi c h a n g e s f r o m 5.5 to co the safe l i m i t i n c r e a s e s by only ~ - 3 ~ C.

60 ergy d e c r e a s e s together with their detonation velocity, whereas their impact sensitivity i n c r e a s e s . 4. The data obtained may prove useful for d e t e r mining the conditions of utilization of explosives at elevated t e m p e r a t u r e s under field conditions. REFERENCES 1. S. A. Lovlya, L, A, Gorbenko, and B. L. Kaplan, Torpedoing and Welt Drilling [in Russian], Moscow, Gostoptekhizdat, 1959. 2. N. N. Semenov, Chain Reactions [in Russian], Leningrad, ONTI, 1934. 3. D. A. F r a n k - K a m e n e t s k i i , Diffusion and Heat

FIZIKA GORENIYA I VZRYVA Transfer in Chemical Kinetics [in Russian], Izd-vo AN SSSR, 1947. 4. V. V. Barzykin and A. G. Merzhauov, DAN SSSR, 120, 1271, 1958. 5. V. V. Barzykin, V. T. Gontkovskaya, A. G. Merzhanov, and S. I. Khudyaev, PMTF, 3, 1964. 6. G. M. Kondrat'ev, Thermal Measurements [in Russian], Mashgiz, 1957. 7. S. I. Khudyaev, Nauchno-tekhnicheskie problemy goreniya i vzryva, 1, 1965.

21 July 1965

Moscow