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Materials and Design 32 (2011) 3361–3369

Materials and Design 32 (2011) 3361–3369 Contents lists available at ScienceDirect Materials and Design journal

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Materials and Design

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Design journal homepage: www.else vier.com/locate/matdes Effect of different curing systems on the mechanical and

Effect of different curing systems on the mechanical and physico-chemical properties of acrylonitrile butadiene rubber vulcanizates

Khaled F. El-Nemr

Radiation Chemistry Dept., National Center for Radiation Research and Technology, AEA, P.O. Box 29, Nasr City, Cairo, Egypt

article info

Article history:

Received 6 October 2010 Accepted 4 February 2011 Available online 26 February 2011

Keywords:

Acrylonitrile butadiene rubber Curing system Mechanical properties

abstract

In the present study, the effect of different curing systems including sulfur, dicumyl peroxide, dicumyl peroxide/coagent and radiation/coagent on the mechanical and physico-chemical properties of acryloni- trile butadiene rubber (NBR) was studied. In order to correlate, the effect of curing systems on rubber, the comparison was carried out at comparable value of volume fraction of rubber in swollen gel (V r ) for NBR vulcanizates. Mechanical properties like tensile strength, elongation at break, modulus, Young’s modulus, tearing strength and abrasion loss of vulcanizates have been followed up for comparison. In addition, physico-chemical properties like swelling ratio, soluble fraction, and cross-link density were investigated. On the other hand, the effects of fuel, thermogravimetric analysis, and thermal ageing have been studied. 2011 Elsevier Ltd. All rights reserved.

1. Introduction

Acrylonitrile butadiene rubber (NBR) has excellent oil resis- tance. However, shows no self-reinforcing effect, as there is no crystallinity, but when used in combination with reinforcing fillers, vulcanizates with excellent mechanical properties can be obtained from NBR [1] . Vulcanization occurs by a chemical agent, such as sulfur or peroxide. Alternatively, high-energy radiation, such as electron beam or gamma radiation can be used to vulcanize rub- bers [2] . The use of organic peroxide as a cross-linking agent through a free radical process is also largely developed. The vulcanization rate is controlled essentially by the decomposition of the peroxide at a given temperature [3] . Compared with sulfur vulcanization, crosslinking by peroxides is a relatively simple process, with phys- ical properties such as high modulus, low compression set and heat ageing properties superior to sulfur cure systems. On the other hand, the peroxide crosslinking has many disadvantages, such as low tensile and tear strength, and flex resistance, which have re- stricted their use in diene rubbers. Many unsaturated rubbers, such as natural rubber (NR), styrene–butadiene rubber (SBR), butadiene rubber (BR), and acrylonitrile butadiene rubber (NBR), contain a varying degree of unsaturation in the polymer backbone or in pen- dant positions. Peroxide radical could potentially react by addition to a double bond or by abstraction of an allylic hydrogen, and both mechanisms occur concurrently in the vulcanization of unsatu- rated elastomers [4] .

National Center for Radiation Research and Technology (NCRRT), 3 Ahmed El-Zomor St., P.O. Box 29, Nasr City, Cairo, Egypt. Tel.: +20 124114780; fax: +20

222749298.

E-mail address: khaledfarouk65@eaea.org.eg

0261-3069/$ - see front matter 2011 Elsevier Ltd. All rights reserved. doi: 10.1016/j.matdes.2011.02.010

The use of coagents in conjunction with peroxides to cure elas- tomers has been common practice in the rubber industry for many years. Coagents are typically multifunctional vinyl monomers that are highly reactive toward free radicals and readily graft to elasto- mer chains to form a complex crosslinked network. These coagents with peroxide are used to improve the physical properties and pro- cessability of peroxide-cured elastomers. Also, they increase not only the crosslinking efficiency of the vulcanization process but the cross-link density as well [5] . During this last decade, the crosslinking of rubbers by means of electron beams has strongly developed in place of the use of cross- linking agents, such as sulfur or peroxides. NBR belongs to the crosslinking type rubbers when exposed to high-energy radiation [6] . Compared with the conventional chemical processes such as peroxide [7] or sulfur [8] induced vulcanization used for crosslink- ing rubber, radiation crosslinking has the advantages of being fas- ter and being more versatile, leads to more uniform crosslinking, consumes less energy, and occupies less floor space for processing. Inherently waste free nature of the technology makes it less polluting than the conventional technologies. The disadvantage is that the physical properties of radiation vulcanized rubber were adversely affected by the high crosslinking dose required. To over- come this problem, several authors [9] have reported that poly- functional monomers PFMs (coagents) such as multifunctional acrylates and methacrylates are useful to obtain optimum mechan- ical properties at lower dose levels. These PFMs form a network structure with polymeric materials at a lower dose because of its higher reactivity [10] and the resulting structure is useful for the improvement of mechanical properties as well as thermal stability [11] . This article is a comparative study between the different tech- niques to vulcanize NBR rubber.

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K.F. El-Nemr / Materials and Design 32 (2011) 3361–3369

2. Experimental

2.1. Materials

Acrylonitrile butadiene rubber (NBR) of Europrene N3345 from Enichem company Inc, Italy having (acrylonitrile content-34%, Mooney viscosity (ML (1 + 4) at 100 C-46). Zinc oxide was sup- plied from Shijiazhuang Golden Color Chemical Co., Ltd., China, its concentration 99.7% in appearance of white powder. Stearic acid obtained from Hebei Liancheng Chemical Co., Ltd., China, it has small flakes shape and melting point 56 C. Dioctyl phthalate (DOP) was supplied by Henan Tianfu Chemical Co., Ltd., China; it has acidity 0.01 maximum and ester value 99.5%. Sulfur was sup- plied by standard chemical company private Ltd., Madras. Mercapto benzothiazyl disulphide (MBTS) was obtained from Bayer India Ltd., Bombay. Tetra methyl thiuram disulphide (TMTD) was supplied by NOCIL, Bombay, India. 1,2-dihydro.2,2,4-trimethyl quinoline (TMQ) as antioxidant was obtained from Intatrade Chemicales (GmbH), Germany.Carbon black (N 375). The peroxide cross-linking agent was dicumyl peroxide [DCP] from Aldrich (Germany), its purity 99%. The polyfunctional monomer PFM (coagent) was penta erythritol triacrylate PETRA from Aldrich with a molecular weight of 298.29 g/mol and a density of 1.167 g/cm 3 .

2.2. Compounding and curing

The compounding recipes of mixes are given in Table 1 , the codes letters S, P, P-PFM and R-PFM represent the sulfur, dicumyl peroxide, dicumyl peroxide coupled with coagent and radiation vulcanized system respectively. The subscript indicates the weight in phr (part per hundred part of rubber) for sulfur, and dicumyl peroxide corresponding to each designation code; while subscript in case of radiation vulcanization indicate the radiation dose. Mixing was carried out at room temperature using a two-roll mixing rubber mill having a friction ratio 1:1.4. The compounded mixes as follow

2.2.1. Sulfur and peroxide curing

The compounded mixes with different amounts of curing sys- tem were compression molded using an electrically heated hydraulic press at 160 C under pressure 120 kg/cm 2 for their opti-

mum curing times i.e. 5 min. for sulfur cured system and 20 min for peroxide and peroxide coupled with coagent cured systems.

2.2.2. Radiation curing

The compounded mixes were compression molded between aluminum foil at 160 C under pressure 120 kg/cm 2 . Irradiation was carried out in air at ambient temperature on the electron beam

accelerator (1.5 MeV, 3 mA) facility installed at the National Center for Radiation Research and Technology, Cairo, Egypt. The irradia- tion was performed to give a total dose of 25 kilo gray (kGy) for each pass. Multiple passes obtained the total irradiation doses 25, 50, 75, 100 and 150 kGy for different measurements.

2.3. Measurements

2.3.1. Mechanical properties

The tensile strength was measured using dumbbell shaped test pieces at a crosshead speed of 500 mm/min at 25 ± 2 C using ten- sile testing machine HOUNS FILD, England. The tearing strength (load at failure/thickness) of the samples was determined using unnicked 90 C angle test pieces according to ASTM D 624-81. The experimental conditions for the tear measurements were the same as that of the tensile testing. The hardness of the samples was measured according to ASTM D 2240-2000 using durometer type A, and the units of hardness was expressed in shore A.

2.3.2. Physico-chemical measurements

2.3.2.1. Soluble fraction. Measurements of soluble fraction were car- ried out as follow, the cured samples, about 0.2 g were accurately weighed ( W o ) and placed in a special stainless grids. The grids con- taining samples are transferred to special round flask 2/3 filled with acetone. The heating was carried out under reflux for 24 h. After extraction, the samples were dried to constant weight ( W 1 ) in dry oven at 50 C. The soluble fraction was calculated as follow:

Soluble fraction ¼ W o W 1 =W o

ð 1Þ

2.3.2.2. Determination of cross-link density ( m ). The volume fraction of rubber in swollen network of the vulcanizates V r , was deter- mined by means of equilibrium swelling in acetone laboratory grade at 25 C. The equilibrium swelling was used to calculate the cross-link density, which is the number of network chain den- sity by applying the Flory–Rehner equation [12] as follow:

m ¼ 1= V s

"

lnð 1 V r Þ þ V r þ v 1 V 2

r

V

1=3

r

V r =2

#

ð 2Þ

density; v 1 = polymer–solvent interaction

parameter; V s = molar volume of solvent; V r = volume fraction of

where, m = cross-link

rubber in the swollen gel; V r was calculated using the relation

V r ¼

ð D s F f A w Þ qr

1

ðD s F f A w Þ qr 1 þ A s qs 1

ð

3Þ

where V r , D s , F f , A w , A s , q r and q s are volume fraction of rubber, deswollen weight of the sample, fraction of insoluble, sample

Table 1 Formulation of the mixes.

Code formulation (phr) *

S 1

S 1.5

S 2

P 1

P 1.5

P 2

P 1 -PFM

P 1.5 -PFM

P 2 -PFM

R 25 -PFM

R 50 -PFM

R 75 -PFM

R 100 -PFM

R 150 -PFM

NBR ZnO Stearic acid TMQ DOP MBTS TMTD Sulfur HAF Peroxide (DCP) PETRA Irradiation dose (kGy)

100

100

100

100

100

100

100

100

100

100

100

100

100

100

5

5

5

5

5

5

5

5

5

5555

5

2

2

22222

2

2

2222

2

1

1

1

1

1

1

1

1

1

1111

1

6

6

6

6

6

6

6

6

6

6666

6

1

1

1––––

––––

0.5

0.5

0.5

––––

1

1.5

2––––

––––

30

30

30

30

30

30

30

30

30

30

30

30

30

30

1

1.5

2

1

1.5

2

––––5

5

5

5555

5

 

25

50

75

100

150

* phr = part per hundred part of rubber.

K.F. El-Nemr / Materials and Design 32 (2011) 3361–3369

3363

weight, weight of the absorbed solvent corrected for swelling incre- ment, density of rubber and density of solvent respectively.

2.3.2.3. Number average molecular weight between crosslinks (M C ). The number average molecular weight between crosslinks ( M C ) was determined according to Flory–Rehner equation as follow

m ¼ 1= 2M C g 1 mol

ð 4Þ

2.3.2.4. Swelling ratio (Q). The swelling ratio ( Q ) was calculated and expressed in terms of the reciprocal of volume fraction of rubber in swollen gel as follow [13,14] :

Q

¼ V 1 =V o ¼ 1= V r

ð 5Þ

where V 1 is the volume of swollen rubber, V o the volume of unswol- len rubber, and V r is the volume fraction of rubber in the swollen gel.

2.4. Thermogravimetric analysis (TGA)

The thermogravimetric analysis (TGA) technique was applied using TG-50 instrument from Shmadzu (Japan). The heating was carried out at temperature to 600 C with a heating rate of 10 C/ min under nitrogen gas atmosphere.

2.5. Effect of fuel

Effect of fuel has been carried out specifically for testing the ef- fect of fuels on polymeric materials. The samples in triplicates were weighed to nearest mg ( M 1 ). They were then transferred to flask 2/3 filled with fuel A (commercial gasoline). Heating has been carried out at 100 C for 22 h. After that, the flask is allowed to cool at room temperature. The samples were then blotted lightly with filter paper to remove the remaining liquid fuel. They were then re- weighed again ( M 2 ) .The percentage change in weight was then calculated using the following equation:

Change in

weight; % ¼ M 2 M 1 100

M

1

2.6. Abrasion measurement

ð

6Þ

Abrasion loss measurement was performed on samples by using an abrasion tester of the type AP.40 (MASCHINEBAU GmbH RAUENSTEIN THURINGEN, Germany). The testes were carried out under the following conditions:

Load = 1 kg. Abrasion path = 40 meter which equivalent to 84 revolutions. The loss in the mass was calculated according to following equation:

Mass loss ðmgÞ

per revolution ¼ W i W f 1000

n

ð

7Þ

where W i is the original mass of sample (gm), W f the final mass of sample (gm), and n is the number of revolutions (84).

2.7. Thermal ageing measurements

The ageing of samples was carried out by keeping the samples in a hot air oven for 24 h at 100 C. Then the samples were condi- tioned at ambient temperature for at least 16 h before mechanical testing was carried out on tensile testing machine HOUNS FILD, England.

3. Results and discussion

3.1. Sulfur vulcanized NBR

The physical properties of NBR composites vulcanized by various ratios of sulfur, keeping accelerator level fixed, are given in Table 2 . The results obtained for the modulus at 100% elongation or tensile modulus ( M 100 ), Young’s modulus ( E o ) and hardness show an increasing trend with increase of sulfur to accelerator ratio, while elongation at break ( E b ) as well as tensile strength (TS) decrease. With increasing sulfur level the number of C A S x A C bonds increases, and is reflected in the values of V r . Moreover, the results of Q , M c , and cross-link density confirmed the formation of crosslink network structure. However, increasing crosslinks over an optimum level cause localized stresses, which results in lower values of TS which we can explained as follow. Tensile strength, unlike the tensile stress at a given elongation and hardness, does not rise continuously with the number of crosslinks. Instead it rises with the number of crosslinks until an optimum is reached, after which if crosslinking is continued (in which case over-crosslinking takes place), it initially falls steeply.

3.2. Peroxide vulcanized NBR

The physical properties of NBR composites cured by different concentrations of DCP, namely, 0.5, 1 and 1.5 phr, are given in Ta- ble 3 . The data have shown that the TS pass through a maximum and then decrease with the increase of DCP content. While, E b diminishes with DCP concentration. Shore A hardness and M 100 values increase with the increase of DCP indicating the increase in cross-link density of the vulcanizates. It is thought that the in- crease of DCP level leads to an increase in the number of C A C bonds [15] , and this is reflected in the values of V r , M c and cross- link density. Decreasing the values of TS by increasing cross-link density, can be explained by the fact that on using DCP the perox- ide radicals can act through abstraction and addition mechanisms. The over-crosslinked domains (or clusters) may experience the highest forces where the network strand will reach a critical force and break [16] .

3.3. Peroxide/coagent cured NBR

NBR composites with different contents of DCP at a fixed con- centration of PETRA, namely, 5 phr was shown in Table 4 . The ob- tained results showed that as DCP increases the M 100 , hardness and cross-link density significally increase. On the other hand, coagents are typically multifunctional vinyl monomers that are highly

Table 2 The physical properties of NBR vulcanized by sulfur.

Formulation

 

S 1

S 1.5

S 2

Mechanical properties Modulus at 100% elongation ( M 100 ), MPa Tensile strength (TS), MPa Elongation at break ( E b ), % Young s modulus ( E o ) Hardness, shore A

2.12

2.30

2.42

17.44

16.00

15.85

1070

739

659

0.92

1.24

1.37

58

60

60

Physico-chemical properties Soluble fraction (SF) Volume fraction of rubber in swollen gel ( V r ) Swelling ratio ( Q ) Molecular weight between crosslink’s ( M c ), g/mol Cross-link density 10 4 ( m = 1/2 M C ), mol/cm 3

0.093

0.081

0.07

0.24

0.28

0.31

4.17

3.56

3.24

1154.5

794.33

636.04

4.37

6.3

7.86

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K.F. El-Nemr / Materials and Design 32 (2011) 3361–3369

Table 3 The physical properties of NBR vulcanized by dicumyl peroxide.

Formulation

 

P 1

P 1.5

P 2

Mechanical properties Modulus at 100% ( M 100 ), MPa Tensile strength (TS), MPa Elongation at break ( E b ), % Young s modulus ( E o ) Hardness, shore A

 

2.18

2.53

3.22

13.41

16.09

13.57

541

481

331

1.23

1.56

2.29

60

63

65

Physico-chemical properties Soluble fraction (SF) Volume fraction of rubber in swollen gel ( V r ) Swelling ratio ( Q ) Molecular weight between crosslink’s ( M c ), g/mol Cross-link density 10 4 ( m = 1/2M C ), mol/cm 3

0.089

0.079

0.072

0.27

0.31

0.34

3.73

3.26

2.94

885.01

646.82

500.07

5.62

7.73

9.98

Table 4 The physical properties of NBR cured by dicumyl peroxide/coagent.

 
 

Formulation

 

P 1 PFM

P 1.5 PFM

P 2 PFM

Mechanical properties Modulus at 100% elongation ( M 100 ), MPa Tensile strength (TS), MPa Elongation at break ( E b ), % Young s modulus ( E o ) Hardness, shore A

Physico-chemical properties Soluble fraction (SF) Volume fraction of rubber in swollen gel ( V r ) Swelling ratio ( Q ) Molecular weight between crosslink’s ( M c ), g/mol Cross-link density 10 4 ( m = 1/2 M C ), mol/cm 3

4.15

4.82

5.90

11.89

12.73

8.84

200

190

133

3.3

3.76

4.88

70

72

75

0.066

0.064

0.06

0.365

0.39

0.42

2.75

2.56

2.38

420.55

354.17

289.84

11.89

14.22

17.25

reactive toward free radicals and graft to elastomer chains to form complex crosslinked network [17,18] . Because of all common coa- gents contain terminal unsaturations, it can be concluded that addition reaction is the principal mechanism by which they react in the compound; this has been confirmed by observed loss of coa- gent unsaturation during peroxide curing [19] . The formation of complex crosslink network has a major impact on decreasing val- ues of TS observed at maximum concentration of DCP. The data ob- tained for V r , Q and M c indicated the increase of cross-link density by values much more when compared by other cured systems like

sulfur and peroxide. The mechanism consists of reactions in the elastomer matrix, in the coagent domains, and between the elast- mer and the coagent. The polymerized coagent radicals are incorporated into the net- work structure by a reaction with the elastomer molecules [20] .

3.4. Radiation/coagent cured NBR

An electron beam accelerator was used to generate free radicals on the carbon atoms of the NBR and coagent. The radicals may either be reacting with each other or grafting on the coagent form- ing crosslinks. Table 5 shows the results for radiation curing of NBR by different radiation doses up to 150 kGy in the presence of 5 phr of PETRA. The M 100 was found to increase linearly with radiation dose indicating the linear relationship of cross-link den- sity with radiation dose, whereas the latter inversely lowers the values of M c . The increase in values of V r , decrease in E b , Q and in solubility were considerable by increasing radiation dose indi- cating the increase of cross-link density of vulcanizate. Also there is an increase in TS up to 100 kGy, beyond which there is a very slight decrease in TS values dose. The leveling off or decrease in TS by radiation may be explained as follows: TS of a polymer is a function of cross-link density and energy dissipation, at higher crosslinking density, i.e. at 150 kGy, the segments of the macro- molecule become immobile, the system becomes stiffer and the elasticity decreases [21] . Also, it can be assumed that the rate of two processes, namely crosslinking and degradation may then oc- cur with the same rate, hindered mobility of macromolecules due to increased rate of crosslinking may contribute also to decreasing the values of TS.

3.5. Physical properties comparison of NBR cured by sulfur, peroxide

and radiation/coagent (100 kGy) at a comparable value of V r

3.5.1. Mechanical properties The V r can be taken as an indicator of cross-link density and reinforcing ability of filler [22,23]. The data listed in the pervious Tables 1–4 , show that the values of V r 0.31, are comparable for NBR cured by 2 phr sulfur, 1.5 phr DCP and radiation/coagent at (100 kGy). For comparison Table 6 represents the respective phys- ical data. Obviously the crosslink structure and cross-link density affect the mechanical properties of NBR vulcanizates depending on the type of curing system. The tear strength, TS and E b values are comparatively the highest in the case of sulfur cured system. The E b data can be explained on the basis that the system can accommodate more stress and elongation via the flexible and labile S-S linkage [24] . The lower tear strength and E b values of DCP cured system are attributed to the short and rigid C A C crosslinks

Table 5 The physical properties of NBR cured by radiation/coagent.

 

Formulation

R 25 PFM

R 50 PFM

R 75 PFM

R 100 PFM

R 150 PFM

Mechanical properties Modulus at 100% elongation ( M 100 ), MPa Tensile strength (TS), MPa Elongation at break (E b ), % Young s modulus (E o ) Hardness, shore A

2.18

2.68

3.5

4.0

5.2

11.2

11.6

13.4

14

13.6

1041

633

540

359

252

0.55

1.06

1.48

2.37

3.49

52

55

60

65

70

Physico-chemical properties Soluble fraction (SF) Volume fraction of rubber in swollen gel ( V r )

0.174

0.14

0.11

0.08

0.06

0.183

0.235

0.285

0.313

0.37

Swelling ratio ( Q ) Molecular weight between crosslink’s ( M c ), g/mol

5.47

4.251

3.513

3.13

2.7

2073

1196.5

776.2

584

402.7

Cross-link

density 10 4 ( m = 1/2 M C ), mol/cm 3

2.41

4.18

6.48

8.48

12.4

K.F. El-Nemr / Materials and Design 32 (2011) 3361–3369

3365

Table 6 The physical properties of NBR cured by sulfur, peroxide and radiation/coagent.

Formulation

 

S 2

P 1.5

R 100 -PFM

Mechanical properties Modulus at 300% elongation ( M 300 ), MPa Modulus at 100% elongation ( M 100 ), MPa Tensile strength (TS), MPa Elongation at break ( E b ), % Young s modulus ( E o ) Hardness, shore A Tearing strength, N/mm

5.81

7.82

10.57

2.42

2.53

4.00

15.85

16.09

14

659

481

359

1.37

1.56

2.37

60

63

65

43

38

27

Physico-chemical properties Soluble fraction (SF)

0.07

0.079

0.08

Volume fraction of rubber in swollen gel ( V r ) 0.31

0.31

0.313

Swelling ratio ( Q ) Molecular weight between crosslink’s ( M c ), g/mol Cross-link density 10 4 ( m = 1/2 M C ), mol/cm 3

3.24

3.26

3.13

636.04

646.82 584

7.86

7.73

8.48

3.13 636.04 646.82 584 7.86 7.73 8.48 Fig. 2. TGA curves of NBR cured by sulfur,

Fig. 2. TGA curves of NBR cured by sulfur, peroxide and radiation/coagent.

between macromolecules chains [24] . The hardness results show slightly higher values in the case of radiation curing system than the others as a result of the associated higher cross-link density. Meanwhile, the lowest tensile strength values compared to those of the peroxide and sulfur cured systems can be related to the loss and isomerization of less relaxed network. On the other hand, the highest reported values of M 100 and M 300 for the radiation/coagent cured system compared to the other systems can be attributed to the cross-link density.

3.5.2. Stress–strain behavior

The stress–strain behavior of NBR demonstrates a remarkable dependence on the applied curing system as shown in Fig. 1 . The initial modulus is almost the same in sulfur and DCP cured sys- tems, however, the DCP system exhibits higher tensile modulus than sulfur though TS values are comparable. Radiation/coagent cured system can accommodate less strength at rupture but exhib- its higher modulus values at any given elongation as a result of the established cross-link density.

3.5.3. Thermal analysis

Fig. 2 shows the TGA thermograms of the NBR composites cured by sulfur, S 2 , peroxide, P 1.5 , and radiation/coagent, R 100 -PFM. The first weight loss stage 150–350 C is due to the loss of a highly

volatile matter, consists of the amount of oil added as a processing agent and a small amount 1–2% of decomposed fragments of the vulcanizing agent (sulfur or peroxide) vulcanization accelerator and antioxidant [25] . The second fraction 350–550 C repre- sented the medium volatile matter, the amount of decomposed polymer. Evidently, the radiation curing system exhibits higher thermal stability than the others as confirmed by the data shown in Table 7 . The differential thermal gravimetric (DTG) curves demonstrate for the three curative systems, only one peak indicating a single stage decomposition in the NBR composite, Fig. 3 , with a consistent

Table 7 Decomposition temperature of NBR cured by sulfur, peroxide and radiation/coagent at different weight losses.

Composition

Temperature ( C)

Weight loss, %

S 2

P 1.5

R 100 -PFM

T 10

415.14

427.00

428.70

T 30

460.00

465.50

461.00

T 50

484.00

486.00

484.00

T 60

497.00

506.00

560.00

T 65

563.00

569.00

580.00

T 70

590.00

590.00

590.00

DTG

484.00

484.00

484.50

590.00 590.00 DTG 484.00 484.00 484.50 Fig. 1. Stress–strain curves of NBR cured by sulfur,

Fig. 1. Stress–strain curves of NBR cured by sulfur, peroxide and radiation/coagent.

of NBR cured by sulfur, peroxide and radiation/coagent. Fig. 3. DTG of NBR cured by sulfur,

Fig. 3. DTG of NBR cured by sulfur, peroxide and radiation/coagent.

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K.F. El-Nemr / Materials and Design 32 (2011) 3361–3369

( T max ) located at 484 C. The relatively higher thermal stability exhibited by the radiation/coagent and peroxide systems is due to the formation of C A C linkages which are more thermally stable than C A S A C and C A S x A C linkages in sulfur vulcanization [26] . Fur- thermore, the C A C linkage in both cured systems possesses a high- er bond energy of 85 k cal mol 1 whereas the bond energy of the S A S crosslink is only 57 k cal mol 1 [27] .

3.5.4. Effect of fuel

NBR rubber is applied specifically as fuel and oil resistant. The resistance can be followed up by measuring the change of weight%, by immersing in fuel A (commercial gasoline) and then plotted as a function of different curing systems, as shown in Fig. 4 . It can be seen that the NBR cured by radiation/coagent gave the best results for swelling resistance in commercial gasoline compared to the

sulfur and peroxide systems at the same V r value. The resistance to swelling can be argued on the basis of the chemical crosslinking magnitude induced in the rubber component by radiation with re- spect to the other methods of curing.

3.5.5. Abrasion resistance

Fig. 5 illustrates the dependence of the abrasion loss in the NBR composite samples on the implemented curing system. Generally, it can be seen that the abrasion loss decreases by the increase in cross-link density. These data indicate that the abrasion resistance

density. These data indicate that the abrasion resistance Fig. 4. Effect of fuel A on the

Fig. 4. Effect of fuel A on the NBR cured by sulfur, peroxide and radiation/coagent.

slightly enhanced in case of radiation/coagent followed by sulfur then peroxide cured systems.

3.6. Physical properties comparison of NBR cured by peroxide/coagent and radiation/coagent (150 kGy) at a comparable value of V r

3.6.1. Mechanical properties

Depending on the data obtained before, Tables 1–4 , comparison can be established between NBR cured by DCP/coagent, (P 1 PFM) with that cured by electron beam radiation/coagent, (R 150 PFM) at comparable values of V r 0.37. The physical properties of the vulcanizates are illustrated in Table 8 . Comparable values for hard- ness, E b , tearing strength, soluble fraction SF, Q , M c and cross-link density were recorded for these two vulcanizates, whereas the vul- canizate samples cured by radiation/coagent gave higher values of TS and tensile modulus. The behavior of the latter is due to the in- crease in cross-link density.

3.6.2. Stress–strain behavior

Fig. 6 shows the stress against strain for NBR cured by DCP/coa- gent and radiation/coagent systems. It can be observed that the radiation/coagent cured samples revealed higher TS and tensile modulus values, the increase in values of TS can be related to the

increase in cross-link density.

Table 8 The physical properties of NBR cured by peroxide/coagent and radiation/coagent.

 

Formulation

P 1 -PFM

R 150 -PFM

Mechanical properties Modulus at 100% elongation ( M 100 ), MPa Tensile strength (TS), MPa Elongation at break ( E b ), % Young s modulus ( E o ) Hardness, shore A Tearing strength, N/mm

Physico-chemical properties Soluble fraction (SF) Volume fraction of rubber in swollen gel ( V r ) Swelling ratio ( Q ) Molecular weight between crosslink’s ( M c ), g/mol Cross-link density 10 4 ( m = 1/2 M C ), mol/cm 3

4.15

5.2

11.89

13.6

200

252

3.3

3.49

70

70

29.2

30

0.066

0.06

0.365

0.37

2.75

2.7

420.55

402.7

11.89

12.4

0.37 2.75 2.7 420.55 402.7 11.89 12.4 Fig. 5. Abrasion loss of NBR cured by sulfur,

Fig. 5. Abrasion loss of NBR cured by sulfur, peroxide and radiation/coagent.

loss of NBR cured by sulfur, peroxide and radiation/coagent. Fig. 6. Effect of peroxide/coagent and radiation/coagent

Fig. 6. Effect of peroxide/coagent and radiation/coagent curing systems on stress– strain behavior of NBR vulcanizates.

K.F. El-Nemr / Materials and Design 32 (2011) 3361–3369

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El-Nemr / Materials and Design 32 (2011) 3361–3369 3367 Fig. 7. TGA curves for NBR cured

Fig. 7. TGA curves for NBR cured by peroxide/coagent and radiation/coagent.

for NBR cured by peroxide/coagent and radiation/coagent. Fig. 8. DTG curves for NBR cured by peroxide/coagent

Fig. 8. DTG curves for NBR cured by peroxide/coagent and radiation/coagent.

Table 9 Decomposition temperature of NBR cured by peroxide/coagent and radiation/coagent.

Composition

Temperature ( C)

Weight loss, %

P 1 -PFM

R 150 -PFM

T 10

428.00

428.00

T 30

466.00

463.35

T 50

488.00

487.00

T 60

526.00

566.75

T 65

593.00

593.00

T 66

600.00

600.00

DTG

486.80

485.00

3.6.3. Thermal analysis

Fig. 7 and Table 9 shows the TGA thermograms and data, respectively, of DCP/coagent and radiation/coagent cured NBR vul- canizates. At temperature up to 500 C both vulcanizates demon- strated similar thermal stability. It can be observed that the decomposition temperatures are nearly comparable for both two cured systems except at 60% decomposition ( T 60 ). The temperature of degradation obtained for radiation/coagent cured system is higher than that of the DCP/coagent cured system, 566.75 C and 526 C respectively. Meanwhile, both cured systems exhibited the same decomposition temperature for 50% loss ( T 50 ) which is fairly close to T max of both vulcanizates, 485 C, as shown by the DTG curves, Fig. 8 . The slight enhancement in thermal stability of radiation/coa- gent cured vulcanizates may be related to a slight increase in cross-link density which is a factor affecting the thermal stability that leads to higher values of activation energy needed for thermal decomposition of vulcanizates [28,29].

3.6.4. Effect of fuel

The impact of the two different curing systems, peroxide/coa- gent and radiation/coagent (150 kGy) on the change in weight% of NBR samples soaked in commercial gasoline is illustrated in Fig. 9 . Evidently, the final weight of the samples cured by radia- tion/coagent is slightly lesser than that of the other ones cured by peroxide/coagent. The results are clearly in good agreement with the results of cross-link density and M c , i.e. the greater the cross-link density, the higher the fuel resistance.

3.6.5. Abrasion resistance

Abrasion resistance of NBR rubber cured by peroxide/coagent and radiation/coagent (150 kGy) is shown in Fig. 10 . It can be

(150 kGy) is shown in Fig. 10 . It can be Fig. 9. Effect of fuel

Fig. 9. Effect of fuel A on the NBR cured by peroxide/coagent and radiation/coagent.

on the NBR cured by peroxide/coagent and radiation/coagent. Fig. 10. Abrasion loss of NBR cured by

Fig. 10. Abrasion loss of NBR cured by peroxide/coagent and radiation/coagent.

noticed that the abrasion resistance of radiation/coagent cured NBR composites is relatively higher than that of those cured by peroxide/coagent system and this behavior may be attributed to the increase in crosslinks induced by radiation.

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K.F. El-Nemr / Materials and Design 32 (2011) 3361–3369

3.7. Effect of thermal ageing

The effect of thermal ageing on the mechanical properties, namely TS, E b and hardness of NBR vulcanizates cured by sulfur, peroxide, peroxide/coagent and radiation/coagent is shown in Figs. 11–13 , respectively. The values of TS for sulfur and radiation/coa- gent (150 kGy) cured systems at 150 kGy were found slightly re- duced on ageing while the other cured systems were not affected. On the other hand, only the values of E b for sulfur cured system decreased on ageing. Meanwhile, the hardness values for all NBR vulcanizates encountered a slight alteration on ageing. The decrease in values of TS and E b in case of sulfur vulcanized samples may be attributed to the fact that the polysulfidic cross- links cleave and rearrange into shorter crosslinks [30] . Also, the de- crease in values of TS of NBR vulcanizates cured by radiation/ coagent may be attributed to chain scission by thermal ageing. Moreover, compared to sulfur vulcanized samples, radiation/coa- gent vulcanized samples are more resistant to heating due to the nature of networks, as C A C linkage is more stable possessing high- er bond energy than C A S A C linkage. It is also well known that polysulfidic linkage is of relatively low bond strength, i.e. poorer thermal ageing resistant.

low bond strength, i.e. poorer thermal ageing resistant. Fig. 11. Effect of thermal ageing on tensile

Fig. 11. Effect of thermal ageing on tensile strength of NBR cured by sulfur, peroxide, peroxide/coagent and radiation/coagent.

by sulfur, peroxide, peroxide/coagent and radiation/coagent. Fig. 12. Effect of thermal ageing on elongation at break

Fig. 12. Effect of thermal ageing on elongation at break for NBR cured by sulfur, peroxide, peroxide/coagent and radiation/coagent.

by sulfur, peroxide, peroxide/coagent and radiation/coagent. Fig. 13. Effect of thermal ageing on hardness of NBR

Fig. 13. Effect of thermal ageing on hardness of NBR cured by sulfur, peroxide, peroxide/coagent and radiation/coagent.

4. Conclusions

The cross-link density of NBR composites increases with increasing the content of sulfur, peroxide, or radiation dose. The cross-link density greatly affects the mechanical properties of vul- canizates, tensile strength go through maximum for every cured system by increasing the vulcanizing agent concentration, thereaf- ter decrease by the over cure. Hardness, Young’s modulus, and modulus at given elongation increased by increasing the cross-link density, while elongation decreased. The physico-chemical proper- ties; like swelling ratio, soluble fraction and M c have been de- creased by increasing the cross-link density. The cured systems of sulfur, 2 phr, peroxide, 1.5 phr and radiation/coagent (100 kGy) for NBR elastomer gave comparable values of V r , 0.31. The sulfur and peroxide cured systems when compared by the radiation/coa- gent system gave slightly higher in values of tensile strength, though of lesser cross-link density and thermal stability. On the other hand, higher values of swelling in fuel and abrasion loss were reported. The radiation/coagent (100 kGy) cured system gave high- er results in thermal stability, thermal ageing, young’s modulus, modulus at given elongation, abrasion resistance and fuel resis- tance than those of the sulfur cured system. The cured systems peroxide/coagent and radiation/coagent (150 kGy) gave compara- ble values of V r , 0.37, and similar values for the physcio-chemical and mechanical properties, except tensile strength reported slightly higher values as a result of irradiation.

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