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# CHAPTER 14

POLYMER STRUCTURES
PROBLEM SOLUTIONS
14.1

Polymorphism is when two or more crystal structures are possible for a material of given
composition. Isomerism is when two or more polymer molecules or mer units have the same
composition, but different atomic arrangements.

## 14.2 The mer structures called for are sketched below.

(a) Polyvinyl fluoride

(b) Polychlorotrifluoroethylene

## (c) Polyvinyl alcohol

107

14.3 Mer weights for several polymers are asked for in this problem.
(a) For polytetrafluoroethylene, each mer unit consists of two carbons and four fluorines (Table
14.3). If A and A represent the atomic weights of carbon and fluorine, respectively, then
C
F
m = 2(A ) + 4(A )
C
F
= (2)(12.01 g/mol) + (4)(19.00 g/mol) = 100.02 g/mol
(b) For polymethyl methacrylate, from Table 14.3, each mer unit has five carbons, eight hydrogens,
and two oxygens. Thus,
m = 5(A ) + 8(A ) + 2(A )
C
H
O
= (5)(12.01 g/mol) + (8)(1.008 g/mol) + (2)(16.00 g/mol) = 100.11 g/mol
(c) For nylon 6,6, from Table 14.3, each mer unit has twelve carbons, twenty-two hydrogens, two
nitrogens, and two oxygens. Thus,
m = 12(A ) + 22(A ) + 2(A ) + 2(A )
N
C
H
O
= (12)(12.01 g/mol) + (22)(1.008 g/mol) + (2)(14.01 g/mol) + (2)(16.00 g/mol)
= 226.32 g/mol
(d) For polyethylene terephthalate, from Table 14.3, each mer unit has ten carbons, eight hydrogens,
and four oxygens. Thus,
m = 10(A ) + 8(A ) + 4(A )
C
H
O
= (10)(12.01 g/mol) + (8)(1.008 g/mol) + (4)(16.00 g/mol) = 192.16 g/mol
14.4 We are asked to compute the number-average degree of polymerization for polypropylene, given
that the number-average molecular weight is 1,000,000 g/mol.
polypropylene is just

108

## The mer molecular weight of

m = 3(A ) + 6(A )
C
H
= (3)(12.01 g/mol) + (6)(1.008 g/mol) = 42.08 g/mol
If we let n represent the number-average degree of polymerization, then from Equation (14.4a)
n

nn =

Mn
m

106 g/mol
= 23, 700
42.08 g/mol

14.5 (a) The mer molecular weight of polystyrene is called for in this portion of the problem. For
polystyrene, from Table 14.3, each mer unit has eight carbons and eight hydrogens. Thus,
m = 8(A ) + 8(A )
C
H
= (8)(12.01 g/mol) + (8)(1.008 g/mol) = 104.14 g/mol
(b) We are now asked to compute the weight-average molecular weight. Since the weight-average
degree of polymerization, n , is 25,000, using Equation (14.4b)
w
Mw = n w m = (25,000)(104.14 g/mol) = 2.60 x 10

g/mol

14.6 (a) From the tabulated data, we are asked to compute Mn , the number-average molecular weight.
This is carried out below.
Molecular wt
Range

Mean M

8,000-16,000

xM
i i

12,000

0.05

600

16,000-24,000

20,000

0.16

3200

24,000-32,000

28,000

0.24

6720

32,000-40,000

36,000

0.28

10,080

40,000-48,000

44,000

0.20

8800

48,000-56,000

52,000

0.07

3640
____________________________

109

Mn =

xiMi

(b) From the tabulated data, we are asked to compute M w , the weight- average molecular weight.
Molecular wt.
Range

Mean M

8,000-16,000

w
i

wM
i i

12,000

0.02

240

16,000-24,000

20,000

0.10

2000

24,000-32,000

28,000

0.20

5600

32,000-40,000

36,000

0.30

10,800

40,000-48,000

44,000

0.27

11,880

48,000-56,000

52,000

0.11

5720
___________________________

Mw =

w iMi

(c) Now we are asked to compute n (the number-average degree of polymerization), using the
n
Equation (14.4a). For polypropylene,

m = 3(A ) + 6(A )
C
H
= (3)(12.01 g/mol) + (6)(1.008 g/mol) = 42.08 g/mol
And
nn =

Mn
m

## 33, 040 g/mol

= 785
42.08 g/mol

(d) And, finally, we are asked to compute n , the weight-average degree of polymerization, which,
w
using Equation (14.4b), is just

110

nw =

Mw
m

## 36, 240 g/mol

= 861
42.08 g/mol

14.7 (a) From the tabulated data, we are asked to compute Mn , the number-average molecular weight.
This is carried out below.

Molecular wt.
Range

Mean M

8,000-20,000

xM
i i

14,000

0.05

700

20,000-32,000

26,000

0.15

3900

32,000-44,000

38,000

0.21

7980

44,000-56,000

50,000

0.28

14,000

56,000-68,000

62,000

0.18

11,160

68,000-80,000

74,000

0.10

7400

80,000-92,000

86,000

0.03

2580
_________________________

Mn =

xiMi

(b) From the tabulated data, we are asked to compute M w , the weight- average molecular weight.
This determination is performed as follows:
Molecular wt.
Range

Mean M

8,000-20,000

w
i

wM
i i

14,000

0.02

280

20,000-32,000

26,000

0.08

2080

32,000-44,000

38,000

0.17

6460

44,000-56,000

50,000

0.29

14,500

56,000-68,000

62,000

0.23

14,260

68,000-80,000

74,000

0.16

11,840

80,000-92,000

86,000

0.05

4300
_________________________

Mw =

111

wiMi

(c) We are now asked if the number-average degree of polymerization is 477, which of the polymers
in Table 14.3 is this material? It is necessary to compute

m =

Mn
n

m in Equation (14.4a) as

## 47, 720 g/mol

= 100.04 g/mol
477

The mer molecular weights of the polymers listed in Table 14.3 are as follows:
Polyethylene--28.05 g/mol
Polyvinyl chloride--62.49 g/mol
Polytetrafluoroethylene--100.02 g/mol
Polypropylene--42.08 g/mol
Polystyrene--104.14 g/mol
Polymethyl methacrylate--100.11 g/mol
Phenol-formaldehyde--133.16 g/mol
Nylon 6,6--226.32 g/mol
PET--192.16 g/mol
Polycarbonate--254.27 g/mol
Therefore, polytetrafluoroethylene is the material since its mer molecular weight is closest to that
calculated above.
(d) The weight-average degree of polymerization may be calculated using Equation (14.4b), since
M w and

nw =

Mw
m

## 53, 720 g/mol

= 537
100.04 g/mol

14.8 This problem asks if it is possible to have a polyvinyl chloride homopolymer with the given molecular
weight data and a number-average degree of polymerization of 1120. The appropriate data are
given below along with a computation of the number-average molecular weight.
Molecular wt.
Range

Mean M

8,000-20,000
20,000-32,000

xM
i i

14,000

0.05

700

26,000

0.15

3900

112

32,000-44,000

38,000

0.21

7980

44,000-56,000

50,000

0.28

14,000

56,000-68,000

62,000

0.18

11,160

68,000-80,000

74,000

0.10

7440

80,000-92,000

86,000

0.03

2580
_________________________

Mw =

xiMi

For PVC, from Table 14.3, each mer unit has two carbons, three hydrogens, and one chlorine. Thus,
m = 2(A ) + 3(A ) + (A )
C
H
Cl
= (2)(12.01 g/mol) + (3)(1.008 g/mol) + (35.45 g/mol) = 62.49 g/mol
Now, we will compute n from Equation (14.4a) as
n

nn =

## 47, 720 g/mol

= 764
62.49 g/mol

Thus, such a homopolymer is not possible since the calculated n is 764 not 1120.
n
14.9 (a) For chlorinated polyethylene, we are asked to determine the weight percent of chlorine added
for 5% Cl substitution of all original hydrogen atoms. Consider 50 carbon atoms; there are 100
possible side-bonding sites. Ninety-five are occupied by hydrogen and five are occupied by Cl.
Thus, the mass of these 50 carbon atoms, m , is just
C
m = 50(A ) = (50)(12.01 g/mol) = 600.5 g
C
C
Likewise, for hydrogen and chlorine,
m = 95(A ) = (95)(1.008 g/mol) = 95.76 g
H
H
m

Cl

Cl

113

## Thus, the concentration of chlorine, C , is just

Cl

CCl =

177.25 g
x 100 = 20.3 wt%
600.5 g + 95.76 g + 177.25 g

(b) Chlorinated polyethylene differs from polyvinyl chloride, in that, for PVC, 1) 25% of the sidebonding sites are substituted with Cl, and 2) the substitution is probably much less random.
14.10

Relative to polymer chains, the difference between configuration and conformation is that

conformation is used in reference to the outline or shape of the chain molecule, whereas,
configuration refers to the arrangement of atom positions along the chain that are not alterable
except by the breaking and reforming of primary bonds.
14.11 This problem first of all asks for us to calculate, using Equation (14.11), the average total chain
length, L, for a linear polyethylene polymer having a number-average molecular weight of 300,000
g/mol.
It is necessary to calculate the number-average degree of polymerization, n , using
n
Equation (14.4a).

For polyethylene, from Table 14.3, each mer unit has two carbons and four

hydrogens. Thus,
m = 2(A ) + 4(A )
C
H
= (2)(12.01 g/mol) + (4)(1.008 g/mol) = 28.05 g/mol
and
nn =

Mn
m

## 300, 000 g/mol

= 10,695
28.05 g/mol

which is the number of mer units along an average chain. Since there are two carbon atoms per mer
unit, there are two C--C chain bonds per mer, which means that the total number of chain bonds in
the molecule, N, is just (2)(10,695) = 21,390 bonds. Furthermore, assume that for single carboncarbon bonds, d = 0.154 nm and = 109 (Section 14.4); therefore, from Equation (14.11)

L = Nd sin

114

= (21, 390)(0.154 nm) sin

109

It is now possible to calculate the average chain end-to-end distance, r, using Equation
(14.12) as
r = d N = (0.154 nm) 21,390 = 22.5 nm

14.12 (a) This portion of the problem asks for us to calculate the number-average molecular weight for a
linear polytetrafluoroethylene for which L in Equation (14.11) is 2000 nm. It is first necessary to
compute the value of N using this equation, where, for the C--C chain bond, d = 0.154 nm, and =
109. Thus

N =

L

d sin

2000 nm

109
(0.154 nm) sin

Since there are two C--C bonds per PTFE mer unit, there is an average of N/2 or 15,900/2 = 7950
mer units per chain, which is also the number-average degree of polymerization, n . In order to
n
compute the value of Mn using Equation (14.4a), we must first determine m for PTFE. Each PTFE
mer unit consists of two carbon and four fluorine atoms, thus
m = 2(A ) + 4(A )
C
F
= (2)(12.01 g/mol) + (4)(19.00 g/mol) = 100.02 g/mol
Therefore
Mn = nnm = (7950)(100.02 g/mol) = 795,000 g/mol

(b) Next, we are to determine the number-average molecular weight for r = 15 nm. Solving for N

115

N =

(15 nm)
=
= 9490
2
d
(0.154 nm) 2

which is the total number of bonds per average molecule. Since there are two C--C bonds per mer
unit, then n = N/2 = 9490/2 = 4745. Now, from Equation (14.4a)
n
Mn = nnm = (4745)(100.02 g/mol) = 474,600 g/mol

14.13 We are asked to sketch portions of a linear polypropylene molecule for different configurations.
(a) Syndiotactic polypropylene

116

## The structure of trans chloroprene is

14.15 This question asks for comparisons of thermoplastic and thermosetting polymers.
(a) Thermoplastic polymers soften when heated and harden when cooled, whereas thermosetting
polymers, harden upon heating, while further heating will not lead to softening.
(b) Thermoplastic polymers have linear and branched structures, while for thermosetting polymers,
the structures will normally be network or crosslinked.
14.16 Thermosetting polyesters will be crosslinked, while thermoplastic ones will have linear structures
14.17 (a) It is not possible to grind up and reuse phenol-formaldehyde because it is a network thermoset
polymer and, therefore, is not amenable to remolding.
(b) Yes, it is possible to grind up and reuse polypropylene since it is a thermoplastic polymer, will
soften when reheated, and, thus, may be remolded.
14.18 This problem asks for sketches of the mer structures for several alternating copolymers.
(a) For poly(ethylene-propylene)

117

## 14.19 For a poly(styrene-butadiene) alternating copolymer with a number-average molecular weight of

1,350,000 g/mol, we are asked to determine the average number of styrene and butadiene mer units
per molecule.
Since it is an alternating copolymer, the number of both types of mer units will be the same.
Therefore, consider them as a single mer unit, and determine the number-average degree of
polymerization. For the styrene mer, there are eight carbon atoms and eight hydrogen atoms, while
the butadiene mer consists of four carbon atoms and six hydrogen atoms. Therefore, the styrenebutadiene combined mer weight is just
m = 12(A ) + 14(A )
C
H
= (12)(12.01 g/mol) + (14)(1.008 g/mol) = 158.23 g/mol
From Equation (14.4a), the number-average degree of polymerization is just

nn =

Mn
m

135,000 g/mol
= 8530
158.23 g/mol

## Thus, there is an average of 8530 of both mer types per molecule.

118

14.20 This problem asks for us to calculate the number-average molecular weight of a random nitrile
rubber copolymer. For the acrylonitrile mer there are three carbon, one nitrogen, and three hydrogen
atoms. Thus, its mer molecular weight is
m

Ac

= 3(A ) + (A ) + 3(A )
C
N
H

## = (3)(12.01 g/mol) + 14.01 g/mol + (3)(1.008 g/mol) = 53.06 g/mol

The butadiene mer is composed of four carbon and six hydrogen atoms. Thus, its mer molecular
weight is
m

Bu

= 4(A ) + 6(A )
C
H

## = (4)(12.01 g/mol) + (6)(1.008 g/mol) = 54.09 g/mol

From Equation (14.5), the average mer molecular weight is just
m = fAcm Ac + fBumBu

## = (0.70)(53.06 g/mol) + (0.30)(54.09 g/mol) = 53.37 g/mol

Since n = 2000 (as stated in the problem), M may be computed using Equation (14.4a) as
n
n
Mn = m nn = (53.37 g/mol)(2000) = 106,740 g/mol

14.21 For an alternating copolymer that has a number-average molecular weight of 100,000 g/mol and a
number-average degree of polymerization of 2210, we are to determine one of the mer types if the
other is ethylene. It is first necessary to calculate

m =

Mn
nn

## 100, 000 g/mol

= 42.25 g/mol
2210

119

Since this is an alternating copolymer we know that chain fraction of each mer type is 0.5; that is f
e
= f = 0.5, f and f being, respectively, the chain fractions of the ethylene and unknown mers. Also,
x
e
x
the mer molecular weight for ethylene is
m = 2(A ) + 4(A )
s
C
H
= 2(12.01 g/mol) + 4(1.008 g/mol) = 28.05 g/mol
Now, using Equation (14.5), it is possible to calculate the mer weight of the unknown mer type, m .
x
Thus

mx =

## 45.25 g/mol - (0.5)(28.05 g/mol)

= 62.45 g/mol
0.5

Finally, it is necessary to calculate the mer molecular weights for each of the possible other mer
types. These are calculated below:
m

## = 8(A ) + 8(A ) = 8(12.01 g/mol) + 8(1.008 g/mol) = 104.16 g/mol

C
H
m
= 3(A ) + 6(A ) = 3(12.01 g/mol) + 6(1.008 g/mol) = 42.08 g/mol
propylene
C
H
m
= 2(A ) + 4(A ) = 2(12.01 g/mol) + 4(19.00 g/mol) = 100.02 g/mol
TFE
C
F
m = 2(A ) + 3(A ) + (A ) = 2(12.01 g/mol) + 3(1.008 g/mol) + 35.45 g/mol = 62.49 g/mol
VC
C
H
Cl
styrene

Therefore, vinyl chloride is the other mer type since its m value is almost the same as the calculated
m .
x
14.22 (a) This portion of the problem asks us to determine the ratio of butadiene to acrylonitrile mers in a
copolymer having a weight-average molecular weight of 250,000 g/mol and a weight-average degree
of polymerization of 4640. It first becomes necessary to calculate the average mer molecular weight
of the copolymer,

120

m =

Mw
n

## 250, 000 g/mol

= 53.88 g/mol
4640

If we designate f as the chain fraction of butadiene mers, since the copolymer consists of only two
b
mer types, the chain fraction of acrylontrile mers f is just 1 - f . Now, Equation (14.5) for this
a
b
copolymer may be written in the form

## m = fbmb + fama = fbmb + (1 - fb )ma

in which m

and m

are the mer molecular weights for butadiene and acrylontrile, respectively.

## These values are calculated as follows:

m = 4(A ) + 6(A ) = 4(12.01 g/mol) + 6(1.008 g/mol) = 54.09 g/mol
b
C
H
m = 3(A ) + 3(A ) + (A ) = 3(12.01 g/mol) + 3(1.008 g/mol) + (14.01 g/mol)
N
a
C
H
= 53.06 g/mol.
Solving for f in the above expression yields
b

fb =

## Furthermore, f = 1 - f = 1 - 0.80 = 0.20; or the ratio is just

a
b

fb
fa

0.80
= 4.0
0.20

(b) Of the possible copolymers, the only one for which there is a restriction on the ratio of mer types
is alternating; the ratio must be 1:1. Therefore, on the basis of the result in part (a), the possibilities
for this copolymer are random, graft, and block.
14.23 For a copolymer consisting of 60 wt% ethylene and 40 wt% propylene, we are asked to determine
the fraction of both mer types.

121

In 100 g of this material, there are 60 g of ethylene and 40 g of propylene. The ethylene
(C H ) molecular weight is
2 4
m(ethylene) = 2(A ) + 4(A )
C
H
= (2)(12.01 g/mol) + (4)(1.008 g/mol) = 28.05 g/mol
The propylene (C H ) molecular weight is
3 6
m(propylene) = 3(A ) + 6(A )
C
H
= (3)(12.01 g/mol) + (6)(1.008 g/mol) = 42.08 g/mol
Therefore, in 100 g of this material, there are

60 g
= 2.14 mol of ethylene
28.05 g / mol
and

40 g
= 0.95 mol of propylene
42.08 g / mol
Thus, the fraction of the ethylene mer, f(ethylene), is just

f(ethylene) =

2.14 mol

2.14 mol

Likewise,

f(propylene) =

0.95 mol

2.14 mol

## 14.24 For a random poly(isobutylene-isoprene) copolymer in which M w = 200,000 g/mol and n =

w
3000, we are asked to compute the fractions of isobutylene and isoprene mers.
From Table 14.5, the isobutylene mer has four carbon and eight hydrogen atoms. Thus,

122

## m = (4)(12.01 g/mol) + (8)(1.008 g/mol) = 56.10 g/mol

ib
Also, from Table 14.5, the isoprene mer has five carbon and eight hydrogen atoms, and
m = (5)(12.01 g/mol) + (8)(1.008 g/mol) = 68.11 g/mol
ip
From Equation (14.5)
m = fibmib + fipmip

## Now, let x = f , such that

ib

m = 56.10x + (68.11)(1 - x)
since f

ib

ip

nw =

Or

3000 =

ib

[56.10x

## f(isoprene) = 1 - x = 1 - 0.12 = 0.88

14.25 (a) For crystalline metals, the individual atoms are positioned in a periodic or ordered arrangement
over relatively large atomic distances. The long-range order in polymer crystals results from the

4
(b) For noncrystalline ceramic glasses, the atomic randomness exists outside the SiO 4 unit. The

## disorder in polymers results from chain misalignment.

123

14.26 The tendency of a polymer to crystallize decreases with increasing molecular weight because as
the chains become longer it is more difficult for all regions along adjacent chains to align so as to
produce the ordered atomic array.
14.27 For each of four pairs of polymers, we are asked to 1) state whether it is possible to decide which
is more likely to crystallize; 2) if so, which is more likely and why; and 3) it is not possible to decide
then why.
(a) No, it is not possible to decide for these two polymers. On the basis of tacticity, the isotactic PP
is more likely to crystallize than the atactic PVC. On the other hand, with regard to side-group
bulkiness, the PVC is more likely to crystallize.
(b) Yes, it is possible to decide for these two copolymers. The linear and syndiotactic polypropylene
is more likely to crystallize than crosslinked cis-isoprene since linear polymers are more likely to
(c) Yes, it is possible to decide for these two polymers. The linear and isotactic polystyrene is more
likely to crystallize than network phenol-formaldehyde; network polymers rarely crystallize, whereas
isotactic ones crystallize relatively easily.
(d) Yes, it is possible to decide for these two copolymers. The block poly(acrylonitrile-isoprene)
copolymer is more likely to crystallize than the graft poly(chloroprene-isobutylene) copolymer. Block
copolymers crystallize more easily than graft ones.
14.28 Given that polyethylene has an orthorhombic unit cell with two equivalent mer units, we are asked
to compute the density of totally crystalline polyethylene.

## In order to solve this problem it is

necessary to employ Equation (3.5), in which n represents the number of mer units within the unit
cell (n = 2), and A is the mer molecular weight, which for polyethylene is just
A = 2(A ) + 4(A )
C
H
= (2)(12.01 g/mol) + (4)(1.008 g/mol) = 28.05 g/mol
Also, V

is the unit cell volume, which is just the product of the three unit cell edge lengths as shown

## in Figure 14.10. Thus,

nA
VC NA

124

(2 mers/uc)(28.05 g/mol)
7.41 x 10 -8 cm

= 0.998 g/cm

3
14.29 For this problem we are given the density of nylon 6,6 (1.213 g/cm ), an expression for the volume
of its unit cell, and the lattice parameters, and are asked to determine the number of mer units per
unit cell. This computation necessitates the use of Equation (3.5), in which we solve for n. Before
this can be carried out we must first calculate V , the unit cell volume, and A the mer molecular
C
weight. For V
C
VC

(0.497)(0.547)(1.729)

## 1 0.441 0.054 0.213 + 2(0.664)(0.232)(0.462)

3
-22
3
= 0.3098 nm = 3.098 x 10
cm
The mer unit for nylon 6,6 is shown in Table 14.3, from which the value of A may be determined as
follows:
A = 12(A ) + 22(A ) + 2(A ) + 2(A )
O
N
C
H
= 12(12.01 g/mol) + 22(1.008 g/mol) + 2(16.00 g/mol) + 2(14.01 g/mol)
= 226.32 g/mol
Finally, solving for n from Equation (3.5) leads to

n =

1.213 g/cm

= 1 mer/unit cell

125

14.30 (a) We are asked to compute the densities of totally crystalline and totally amorphous polyethylene
[ and from Equation (14.10)]. From Equation (14.10) let C = (% crystallinity)/100, such that
c
a

C =

## Rearrangement of this expression leads to

c ( Cs s ) + c a Csa = 0

in which and are the variables for which solutions are to be found. Since two values of and
c
a
s
C are specified in the problem, two equations may be constructed as follows:
c ( C1 s1 s1 ) + c a C1s1 a = 0
c ( C2 s2 s2 ) + c a C2 s2 a = 0

In which

s1

3
= 0.965 g/cm ,

s2

= 0.925 g/cm

3,

## C = 0.768, and C = 0.464. Solving the above

1
2

a =

s1 s2 (C1 C2 )
C1 s1 C2 s2

0.965 g/cm

And

c =

s1 s2 ( C2 C1)
s2 (C2 1) - s1 (C1 1)

0.965 g/cm

126

## (b) Now we are to determine the % crystallinity for

3
= 0.950 g/cm . Again, using Equation

(14.10)

% crystallinity =

0.998 g/cm

= 65.7%
14.31

(a)

We are asked to compute the densities of totally crystalline and totally amorphous

polypropylene [

and

% crystallinity
,
100

such that

C =

## Rearrangement of this expression leads to

c ( Cs s ) + c a Csa = 0

in which and are the variables for which solutions are to be found. Since two values of and
c
a
s
C are specified in the problem, two equations may be constructed as follows:
c ( C1 s1 s1) + c a C1 s1a = 0
c ( C2s2 s2 ) + ca C2s2a = 0

In which

s1

3
= 0.904 g/cm ,

3
= 0.895 g/cm , C = 0.628, and C = 0.544. Solving the above
s2
1
2

127

a =

s1 s2 (C1 C 2 )
C1 s1 C 2s2

0.904 g / cm

And

c =

s1s2 ( C2 C1)
(C 1) ( C 1)
s2 2
s1 1

0.904 g/ cm

(b) Now we are asked to determine the density of a specimen having 74.6% crystallinity. Solving for
from Equation (14.10) and substitution for and which were computed in part (a) yields
s
a
c

s =

c a
C (c a ) c

= 0.917 g/cm

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