2012-Mechanical and Thermal Properties of FPMPHACMACM Blends

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2012 44: 533 originally published online 27 May 2012Journal of Elastomers and PlasticsHuang Yanmin, Liu Lan, Chen Juanjuan, Luo Yuanfan and Jia Demin

Mechanical and thermal properties of FPM/PHACM/ACM blends

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Article

Mechanical andthermal properties ofFPM/PHACM/ACMblends

Huang Yanmin, Liu Lan, Chen Juanjuan,Luo Yuanfan and Jia Demin

AbstractThe bisphenol AF/benzyltriphenylphosphonium chloride (BPP) vulcanization systemis the most commonly used fluoroelastomer (FPM) vulcanization system. In thisarticle, polyphenol hydroxy acrylic rubber (PHACM) was prepared through a two-step reaction: grafting polymerization and condensation. The properties of FPM/PHACM/acrylic rubber (ACM) blends including vulcanization properties, mechanicalproperties, aging properties, oil resistance and thermal properties were studied. Theresults of vulcanization properties show that under the bisphenol AF/BPP vulcaniza-tion system, the FPM can achieve covulcanization with PHACM without addingbisphenol AF and get longer scorch time than that of FPM with the same level ofbisphenol AF, which means that FPM/PHACM/ACM blends have better processabil-ity and curing security. Furthermore, the blends show better mechanical propertiesand thermal stability. The results of differential scanning calorimeteric analysis showthat the FPM and PHACM achieve co-cross-linking and have good compatibility. Theglass transition temperature (Tg) of the blends has been reduced to 18.57C,which is 8.33C lower than that of pure FPM, when the content of blends is equalto 100/100. The scanning electron microscopy shows that PHACM can improveinterfacial adhesion between the FPM and ACM.

KeywordsFluoroelastomer, PHACM, blend, co-vulcanization

College of Material Science and Engineering, South China University of Technology, Guangzhou, China

Corresponding author:

Liu Lan, College of Material Science and Engineering, South China University of Technology, Guangzhou

510640, China

Email: [email protected]

Journal of Elastomers & Plastics

44(6) 533548

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Introduction

Fluoroelastomers (FPMs) constitute one of the most important classes of synthetic

rubbers and are well known for their inherent resistance to fuel, oil and heat, owing to the

strong nature of their structural chemistry (i.e. CF bond energy 485 kJ mol1).1,2FPMs are widely applied in many industrial fields due to their fabulous heat-, oil- and

solvent-resistant properties.38 The application of FPM in automobile, aerospace and

energy-related industries implies that it is in accordance with the excellent product per-

formance standards under severe chemical environments.911 However, the existing dis-

advantages of FPM, such as poor process property and the lack of low-temperature

resistance, prevent it from further application. Thus, it is important to focus on enlarging

the application range of FPM, especially on the field of low temperature.

Acrylic rubbers (ACM) own excellent performance on fields of heat-resistance, oil-

resistance, ozone-resistance and excellent process property; and it is relative low price

(about 10% of FPM). ACM, called auto-used rubber,12,13 is mainly used in the auto-mobile industry. It is demonstrated that ACMs and FPMs are thermodynamically misci-

ble.1416 Thus, it is possible to fabricate FPM/ACM blends which are known for both its

low price and its high performance.

However, these two polymers use different types of vulcanization system. It is nec-

essary to find a common vulcanization system in order to obtain excellent rubber vul-

canization. The rheological and mechanical properties of ACM/FPM blends17 and a

thermoplastic elastomer derived from the blending of ACM/FPM and multifunctional

acrylates have been reported.18 It is learned that the good rheological and mechanical

properties were achieved using the amine compounds vulcanization system. However,

the blends exhibit shortage of permanent compression set property and heat-resistant

property using the amine compounds vulcanization system instead of the bisphenol

AF/benzyltriphenylphosphonium chloride (BPP) vulcanization system. Nothing has

been published in the literature on the vulcanizing characteristics and mechanical and

thermal properties of FPM/ACM blends under bisphenol AF/BPP vulcanization system.

The permanent compression set property is one of the important indexes representing

sealing property and life span of rubber products. The blends under bisphenol AF/BPP

vulcanization system achieve better permanent compression set property than those

under amine vulcanization system, because it is easy for amine blends, whose cross-

linking bond is CN bond, to get rid of Hydrogen fluoride (HF) to form CN structureunder high-temperature condition. The CN bond can be easily hydrolyzed to COstructure that in turn could re-cross-link under high temperature. The intertransformation

between break of cross-linking and re-cross-linking results in the decrease of permanent

compression set property of the blends. However, the bisphenol cross-linking is com-

posed of CO cross-linking that owns high chemical and thermal stability, improving

heat resistance and permanent compression set property of the blends.

In this article, ACM was graft modified by bisphenol A to prepare polyphenol

hydroxy acrylic rubber (PHACM), and the properties of FPM/ACM/PHACM blends

including vulcanizing, mechanical, aging, oil-resistant and heat-resistant properties were

studied. It is expected to form a new type of blend that has both excellent performance

534 Journal of Elastomers & Plastics 44(6)



and low price. This can provide scientific foundation for the application of high-

performance FPMs on civil use, especially on automobile industry.

Experimental

Materials

FPM (copolymer of vinylidene fluoride and hexafluoropropylene), FPM-2603 (66% F;density: 1.811.84 g cm3), was obtained from Chenguang Chemical Co. Ltd (Sichuan,China). PHACM was self-prepared. The bisphenol A and BPP were supplied by Dupont

Dow (Wilmington, Delaware, USA). The Ca(OH)2, MgO and silane coupling agents

were supplied by Guangzhou Rubber Institute (China). Carbon black N990 was supplied

by Qingdao Degusa Chemical Co. Ltd.

Preparation of PHACM

For preparing PHACM, first, 30 g of ACM and 4 g of silane coupling agent and

appropriate toluene were added into flask and stirred for 30 min at room temperature.20

Second, 1 g Benzoyl Peroxide (BPO) initiator was added and stirred for 1 h at 90C.Then, appropriate content of zinc stearate and 23.15 g bisphenol A was added to con-

densate at 90C. At last, PHACM was prepared by steaming the solvent.

Preparation of FPM/PHACM/ACM blends

The blends were prepared in a 160 330 open two-roll mill. The rollers ran at a speedratio of 1:1.22 (front roller:back roller). The FPM/ACM/PHACM blends are showed in

Table 1. The PHACM was substituted by bisphenol A for pure FPM. The blends were

vulcanized in a hydraulic press at a pressure of 5 MPa for 10 min (10 min was in excess

of the optimum vulcanization time of about 5 min, which was determined from the oscil-

lating disc rheometer). The molded samples were postvulcanized at 200C for 5 h.

Measurements

Fourier-transform infrared (FTIR)-attenuated total reflection (ATR) spectra of the samples

before and after vulcanization were measured on a Nicolet FTIR spectrophotometer

Table 1. Blends formulations (phr)

1# 2# 3# 4# 5# 6# 7#

FPM/(PHACM ACM) 100/0 100/20 100/40 100/60 100/80 100/100 0/100FPM 100 100 100 100 100 100 0PHACM ACM 0 0 6 14 7 33 8 52 9 71 10 90 0 100Bisphenol A 2 0 0 0 0 0 2

PHACM: polyphenol hydroxy acrylic rubber; ACM: acrylic rubber; FPM: fluoroelastomer.19

Other ingredients: MgO: 3 phr; Ca(OH)2: 6 phr; N990: 20 phr; BPP: 0.4 phr.

PHACM is 40%.

Yanmin et al. 535



(Madison, Wisconsin, USA) from 4000 to 550 cm1 in 4 cm1 resolution. For each sample,three scans were taken to identify the peaks. The 1H nuclear magnetic resonance (NMR) was

tested by Bruker-400 MHz NMR (Stuttgart, Baden-Wurttemberg, Germany) using chloro-

form as a solvent and tetramethylsilane (TMS) as an internal standard. The vulcanization

characteristics of the blends were studied using a UR-2030SD rheometer (U-CAN Technol-

ogy Co. Ltd, Taiwan) at 170C. Tensile and tear testing were performed on samples cut from1-mm-thick sheet and tested using a UT-2080 electron tensile tester (U-CAN Technology

Co. Ltd, Taiwan), according to GB/T 528-1998 and GB/T 529-1999, respectively. Shore

A hardness was measured according to GB/T 531-92, oil-resistant testing was performed

at 150C for 72 h using ASTM 3# standard oil in GT-80407 constant temperature tank (Tai-wan Gotech Co. Ltd, Taiwan) according to GB/T 1690-92. Thermal oxidative age testing

was performed at 200C for 168 h using GT-7017-M age tester (High-iron detect instrumentCo. Ltd, donguan, Guangzhou, China), according to GB/T 3512-2001. Cross-linking den-

sity was determined by equilibrium swelling method. The samples were swollen in hexane

at room temperature to an equilibrium state and then removed from the solvent, and the hex-

ane on the surface was quickly blotted off with tissue paper. The samples were immediately

weighed on an analytical balance to the tolerance of 1 mg and then dried at vacuum, assum-

ing that the mass loss of the rubber during swelling is the same.

For all the samples, the volume fraction of rubber in swollen gel (Vr), which was used

to represent the cross-linking density of the vulcanizates, was determined by the follow-

ing equation

Vr 1

1 mbma

1

rswhere ma and mb is the sample masses before and after swelling, respectively, r and s is thedensity of rubber and solvent, respectively, and a is the mass fraction of rubber in thevulcanizates. The glass transition temperature (Tg) was carried out with a Nicolet differential

scanning calorimeter (DSC, Madison, Wisconsin, USA). Temperature calibration was

performed with indium as a standard. The DSC runs were made on samples of about 5 mg in

a stream of nitrogen (40 mL min1). Before each thermal measurement, the samples werecooled rapidly (20C per inch) to60C and maintained at this temperature for 3 min. Then,the samples were heated quickly to 100C and held for 3 min. The morphology of thecomposites was investigated by Philips XL-30FEG scanning electron microscope (SEM,

Oregon, USA). Specimens were fractured after immersing in the liquid nitrogen for 1 min.

The fractured surfaces were sputter coated with gold.

Results and discussion

Characterization of PHACM

PHACM was prepared by grafting bisphenol A on ACM in the solution method. The

prepared PHACM was then extracted to get rid of unreactive reactant including

bisphenol A and KH-570 and BPO. The grafted ratio of PHACM is about 15.23%.




As shown on Figures 1 and 2, the FTIR spectra of ACM, PHACM, bisphenol A and

silane coupling agent KH-570 were treated and analyzed. It is observed that there are

obvious difference in the molecular structure difference between ACM and PHACM.

For ACM, characteristic absorption peak of 1729 cm1 belongs to the ester carbonylstretching vibration absorption peak; and for PHACM, there contains SiO bond,

hydroxy, and benzene ring structure. Hence, the characteristic absorption peak of

3400 cm1 represents the phenolic hydroxy vibration absorption peak of PHACM, andthe absorption peaks appeared from 1600 to 1400 cm1 relate to the benzene ring onthe side chain of PHACM, the absorption peaks appeared from 1101 to 1079 cm1

relate to the SiO bond on the side chain of PHACM. It is learned from the above anal-

ysis that the silane coupling agent KH-570 and bisphenol A have been grafted on to the

PHACM successfully.

1H NMR spectra. The extracted PHACM was analyzed by NMR and was comparedwith NMR spectra of ACM. From Figure 3, it is observed that there exists the charac-

teristic peak of 7.1 ppm, which represents the existence of benzene, and the characteristic

peak of 9.2 ppm, which represents the existence of H atom on phenol hydroxyl group.

This indicates that PHACM contains silane coupling agent KH-570 and bisphenol A,

proving the successful preparation of PHACM.

The graft reaction of PHACM is as follows.

1. Free radicals were generated on molecular chains when the active points of rubber

chains were attacked by initiator21 as shown in Figure 4(a).

Figure 1. FTIR spectra of ACM and PHACM.

Yanmin et al. 537



Figure 3. 1HNMR spectrums of ACM and PHACM.

Figure 2. FTIR spectra of Bisphenol A, KH-570 and PHACM.




2. Graft reaction on CC of silane coupling agent KH-570 was triggered by freeradicals, generating ACM rubber side chain as shown in Figure 4(b) and (c).

3. Condensation reaction involving the reaction of the side chain of ethoxy with

phenolic hydroxy of bisphenol A,22,23 as shown in Figure 4(d).

Vulcanization properties of blends

The vulcanization character of FPM/ACM/PHACM blends with different contents was

studied in order to analyze whether ACM and PHACM can covulcanizate with FPM

under the bisphenol A/BPP vulcanization system. Figure 5 shows the vulcanization

curves of blends with different contents (Table 2).

From Figure 5, it is observed that FPM/PHACM/ACM blends can covulcanizate

without the addition of vulcanization agent bisphenol A. The graft of phenol

hydroxy on PHACM makes it easy for FPM and PHACM to covulcanizate together.

When FPM/PHACM/ACM blends are equal to 100/6/14 and 100/7/33, the scorch

time of the blends prolongs a little and the vulcanization time T90 enhances in a

great degree, indicating that the addition of a few percentage of PHACM can

improve the scorching quality of the blends. The main reason is that the vulcani-

zation rate of PHACM is comparatively low under the bisphenol A/BPP vulcani-

zation system, just equaling to one-eighteenth of vulcanization rate of FPM.

Therefore, vulcanization rate of blends decreases in a large degree with the addition

of PHACM. The decrease in the value of MH-ML with the addition of ACM is due

to the low ML value of pure ACM.

Figure 4. The reaction progress of PHACM.

Yanmin et al. 539



Mechanical properties of blends

The mechanical properties of blends as a function of PHACMACM content are shown inTable 3. Table 3 shows that each property of the blends has improved with the addition of

PHACM ACM, compared with pure FPM rubber.The change trend of 100% stretchingstress and hardness of blends is basically the same as the change in blend cross-linking den-

sity. Both 100% stretching stress and hardness of blends increase with the increase in cross-linking density. The 100% stretching stress of blends reaches a maximum when the contentof PHACM ACM is 40%. Other properties of blends increase with increase inPHACM ACM content, and the change in tear strength property is the most significant.

The permanent compression set property of the blends, which is lower than that of

pure FPM, enhances with the addition of ACM, meaning fine permanent compression set

Figure 5. Vulcanization curves of blends.

Table 2. Vulcanization properties of the blends

1# 2# 3# 4# 5# 6# 7#

FPM/(PHACM ACM) 100/0 100/20 100/40 100/60 100/80 100/100 0/100t10 (min) 1.58 2.13 1.75 1.65 1.63 1.58 1.55t90 (min) 3.75 21.75 23.17 30.30 33.00 34.42 41.33ML (dN m) 3.61 2.75 3.56 3.69 3.92 4.00 4.22MH (dN m) 32.50 29.93 28.11 23.98 21.22 20.52 14.65MH-ML (dN m) 28.89 27.18 24.55 20.29 17.30 16.52 10.43Vulcanization rate (min1) 46.14 5.10 4.62 3.48 3.18 3.06 2.52

PHACM: polyphenol hydroxy acrylic rubber; ACM: acrylic rubber; FPM: fluoroelastomer; MH: the highest value of

momentoftorque; ML: the lowest value of momentoftorque; MH-ML: the difference value between MH and ML.




property of the blends under the bisphenol A/BPP vulcanization system. At the same

time, addition of PHACM into blends enhances the reactive force between FPM and

ACM morphology, forming entangled network structure and significantly improving the

mechanical properties of blends.

Oil-resistant property

The oil resistance testing was carried out at 150C for 72 h, and the mechanical prop-erties and weight change ratio of blends were investigated in 3# standard oil, so as to

evaluate the aging property of the blends at oil-resistant atmosphere.

The weight change ratio reflects the weight stability of rubber material in oil-

resistant atmosphere. Rubber material is required to own small weight change ratio,

especially when it is applied to make components in oil environment such as oil

seal. Table 4 and Figure 6 show the weight change ratio of blends in ASTM 3# standard

oil atmosphere, the weight change ratio of pure FPM equals to 1.1%, representingexcellent weight stability of pure FPM. The weight change ratio becomes larger and

larger with increase in ACM PHACM content of the blends. The main reason is thatthe oil-resistant property of FPM is much better than that of ACM PHACM. So theoil-resistant property of the blends shows a decreased trend.

From Table 5, it is observed that all the mechanical properties of swollen blends

decreased when compared with that of the blends. The CF breaks continuously during

the aging process. The broken F can react with the additives of the blends, generatingnew ionic-type fluoride, which leads to decrease in the oil-resistant property of the

blends during the aging process.24

The tensile property, elongation break and weight change ratio first decreases and then

enhances with the addition of ACM PHACM content. Generally speaking, 3# blendachieves the best oil-resistant property. This is mainly because molecular chain and cross-

linking bond of the blends break due to the coaction of oil as a medium and heat. The

higher cross-linking density of 3# blends results in its better oil-resistant property.

Cross-linking density of the blends

From Figure 7, it is learned that the apparent cross-linking density of the blends firstly

enhances and then decreases with the addition of blends content. When the blends con-

tent is 100/40, the apparent cross-linking density curves show a peak (Table 6); however,

Table 3. Mechanical properties of the blends

1# 2# 3# 4# 5# 6# 7#

Tensile strength (Mpa) 10.88 10.35 11.46 12.27 12.86 11.30 16.55Elongation break (%) 182.38 183.80 189.55 196.53 207.37 234.00 484.70Stress at 100% strain (Mpa) 4.93 6.22 7.60 6.58 6.65 5.66 5.24Tear strength (kN m1) 23.47 24.53 26.03 30.49 32.39 34.53 62.59Shore A hardness 65 64 65 67 66 65 67Permanant compression set (%) 23 30 38 42 45 50 69

Yanmin et al. 541



the maximum apparent cross-linking density is found at 7#, the pure ACM. It could be

investigated that the ACM rubber can self-vulcanizate under the bisphenol A/BPP vul-

canization system and achieve high apparent cross-linking density. Although the vulca-

nization rate of ACM was very low during vulcanization process, it can vulcanize totally

Table 4. Change in blends weight before and after swelling

Number Before swelling m1 (g) After swelling m2 (g) m (%) Average value of m (%)

1# 1 0.8996 0.9095 1.10 1.12 0.8864 0.8961 1.093 0.9101 0.9204 1.13

2# 1 0.8013 0.8734 9.00 9.22 0.8184 0.8955 9.423 0.8296 0.9048 9.06

3# 1 0.8835 0.9810 11.04 11.32 0.9067 1.0087 11.253 0.8345 0.9302 11.47

4# 1 0.7985 0.9039 13.20 13.42 0.8132 0.9227 13.473 0.8663 0.9827 13.44

5# 1 0.8389 0.9791 16.71 16.62 0.8234 0.9604 16.643 0.8802 1.0245 16.39

6# 1 0.7668 0.9241 20.51 20.32 0.7648 0.9192 20.193 0.7722 0.9280 20.18

Figure 6. Change of blends weight.




during the post vulcanization process and reaches a high apparent cross-linking density.

The change in trend of apparent cross-linking density is perfectly same as the change in

trend of mechanical properties and oil-resistant property, meaning that the apparent

cross-linking density is one of the most important influencing factors of the properties

of rubber.

Table 5. Mechanical properties of the blends after oil resistance testing (150C 72 h)

1# 2# 3# 4# 5# 6#

Tensile strength (MPa) 10.36 10.03 11.17 11.79 12.15 10.69Change ratio of tensile strength (%) 4.78 3.14 2.53 3.91 5.52 5.40Elongation break (%) 154.89 170.48 172.81 169.99 176.36 159.93Change ratio of elongation break (%) 15.07 7.25 8.83 13.5 14.95 31.65Shore A hardness 55 62 63 60 57 53Change ratio of hardness (%) 5.17 3.13 3.08 10.45 13.64 18.46

Figure 7. Apparent cross-linking density curves of blends.

Table 6. Cross-linking density of the blends

1# 2# 3# 4# 5# 6# 7#

Apparent cross-linking density 0.255 0.286 0.304 0.289 0.293 0.285 0.313

Yanmin et al. 543



Tg of blends

From Table 7, it is found that Tg of pure FPM is 10.24C and Tg of pureACM is 20.30C. The Tg of FPM/ACM/PHACM blends reduces continuously withthe addition of ACM content. The Tg value of the blends is between the Tg value of

pure FPM and pure ACM, indicating that the addition of ACM decreases the Tg of

blends, thereby resulting in the low-temperature properties of blends. The Tg of blends

reduce to 18.57C, which is 8.33C lower than that of the pure FPM, when thecontent of blends equals to 100/100. From Figure 8, it is found that only one Tg of

FPM/ACM/PHACM blends exists, representing fine miscibility of FPM phase and

ACM phase.

Thermal property of the blends

The Tg experiment of 1#, 2#, 4#, 6# and 7# blends was carried out, and from Figure

9, it is found there are two weight loss steps. The two weight loss steps of blends

Table 7. Glass transition temperature (Tg) of the blends

1# 2# 3# 4# 5# 6# 7#

Tg (C) 10.24 12.05 14.60 16.43 17.59 18.57 20.30

Figure 8. DSC spectra of blends.




are less significant than corresponding weight loss steps of pure FPM(1#), indi-

cating that existence of PHACM could improve the interface action of FPM and

ACM. The miscibility of FPM and ACM has obviously improved with the addition

of PHACM.

Table 8 shows that the existence of first weight loss step is because of

thermal decomposition of ACM; the second decomposition temperature belongs to

thermal decomposition of FPM, whose maximum weight loss temperature is nar-

rowly higher than the pure FPM, meaning that the cross-linking network formed

between PHACM and FPM enables the thermal stability of the blends. The 5%,10%, 20% and 50% weight loss temperature of blends are lower than that of pureFPM and are higher than that of pure ACM, showing blends still own fine thermal

stability and excellent miscibility.

Figure 9. TG curves of blends.

Table 8. Thermal stability of the blends

1# 2# 4# 6# 7#

5% Weight loss temperature (C) 416.28 388.40 378.24 374.82 363.4510% Weight loss temperature (C) 431.88 410.55 400.91 396.69 384.7620% Weight loss temperature (C) 448.21 434.86 423.40 416.90 400.6550% Weight loss temperature (C) 472.41 477.28 471.68 464.53 436.23Maximum weight loss temperature (C) 472.06 428.77 425.46 425.94 413.00

477.35 474.47 474.54

Yanmin et al. 545



Scanning electron microscope

From Figures 10 and 11, it is observed that the blends including PHACM own

better uniform morphology, meaning addition of PHACM can improve interfacial

adhesion between FPM and ACM. The main reason is that both FPM and PHACM are

polar, so they are miscible thermodynamically. Covulcanization between FPM and

PHACM generate cross-linking network structure, which easily results in excellent mis-

cible blends.

Conclusions

PHACM rubber was successfully prepared by the solution method, in which

the structure of PHACM was characterized and the structure and properties of

the blends were studied. It is discovered that there exists a grafted phenol hydroxy

structure on PHACM, which could participate in vulcanization. The FPM/ACM/

PHACM blends achieve covulcanization and get better mechanical properties including

tensile strength and elongation break ratio than pure FPM. The blends own better antia-

ging, oil resistance and thermal stability. The Tg of FPM/ACM/PHACM blends with 100/

100 content reduce by 8.33C than that of pure FPM. It is learned that the addition ofPHACM improves interfacial adhesion between the FPM phase and ACM phase.

Figure 10. SEM of FPM /ACM blends.




Funding

This work was supported by the National natural science foundation of China (contract

grant number: 50873036) and the Fundamental Research Funds for the Central Uni-

versities, SCUT (2009ZM0306).

Acknowledgements

The authors thank the College of Material Science and Engineering of South China University of

Technology for supporting the group in undertaking the project.

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2012-Mechanical and Thermal Properties of FPMPHACMACM Blends