T. Zaharescu et al.

/ Journal of Advanced Research in Physics 1(1), 011012 (2010)

Qualification of ethylene-propylene elastomers for nuclear applications

Traian Zaharescu1*, Silviu Jipa2, Adrian Mantsch1, Istvan Borbath3, and Tunde Borbath3
1

INCDIE ICPE CA, 313 Splaiul Unirii, Bucharest 030138 Valahia University, Faculty of Sciences and Arts, 18-22 Unirii Av., Targoviste 130082 3 ROSEAL S. A., 5/A N. Balcescu St., Odorheiu Secuiesc, Harghita 535600
2

Abstract This paper studies the radiation stability of ethylene-propylene terpolymer subjected to radiation degradation under various stabilization states. Two sorts of elastomers were tested free of stabilizer or in the presence of phenolic antioxidants: IRGANOX 1010 and ETHANOX 330. The additive concentration of 2 % places polymers under high stabilization state. Low dose rate (0.04 and 0.4 kGy/h) was applied for the simulating of real parameters of material ageing. The qualification of elastomers was managed by mechanical investigation, FTIR spectroscopy and chemiluminescence. The presence of used antioxidants offered a remarkable resistance to the action of -radiation (137Cs) emphasizing the preservation of either physical and chemical properties, or integrity of neat materials. Keywords ethylene-propylene elastomers, gamma irradiation, low dose rate, phenolic antioxidants, spectroscopy, chemiluminescence

I.

INTRODUCTION

Technical and economical problems arising from the operation environment on polymer durability have been received a special attention because of the security of nuclear power plants. The polymer items that are used as sealant, membranes, O-rings, gaskets, electrical insulations, hoses, coatings, vibration mountings and many others must be previously tested according with the real operation conditions [1]. The degradation of polymer materials takes always place which is accelerated by the transfer of energy under mechanical stress, chemical attack, radiation exposure or any hard conditions. The action of ionizing radiation is the most important aspect concerned for the plastics usage in various components of nuclear equipments. The degradation of polymer products is of considerable interest and, therefore, several surveys have been reported [2-5]. The progress in oxidative degradation of polymers depends on several factors, i.e. absorbed dose, dose rate, exposure environment, energy of incidental radiation,
Manuscript received June 07, 2010. * Corresponding author (zaharescu@icpe-ca.ro)

chemistry of material, previous state of ageing. The radiation ageing of polymers offers the advantage of fast material qualification, which involves the resistance of samples to the action of stressors. The mitigation of degradation can be accomplished either by previous curing or by the addition of stabilizing compounds. If in the first alternative the degrading material may be applied to a restricted class of polymers, the second procedure ensures the long term stability in direct correlation with the antioxidant efficiency. The action of stabilizers is a preventive activity through which free radicals formed during exposure are generated. The scavenging action of additives blocks the reaction of hydrocarbon fragments with the molecular oxygen diffused inside the material from surrounding environment. These compounds protect reactive radicals, which can survive for long period or they can react to each other for achieving a higher crosslinking. Under high energy irradiation several oxygenated products are formed, their concentrations depend on the chemical nature of polymer substrate and the activity of antioxidant [6, 7]. Several investigations on ethylene-propylene elastomers were performed for characterization of radiation resistance of this kind of plastic materials [8-15]. These contributions have emphasized the availability of elastomers for maintaining initial properties or for crosslinking during the exposure to ionizing radiation. This favorable behavior springs from the overunit value kept by the ratio between crosslinking radiochemical yield and scission one. The selection of suitable and effective antioxidant, attention must be paid to the nature of antioxidant, its compatibility with host polymer, toxicity, volatilization during processing, influence on the stability of polymer and the resultant degradation products. During the radiolysis of polymer (in our paper, ethylenepropylene terpolymer, EPDM), the mechanisms of backbone scission and oxidative degradation are simultaneously occured [16]. The efficiency of added antioxidants is demonstrated by the preservation of initial features of pristine material. In this paper the efficiency of two phenolic antioxidants (IRGANOX 1010 and ETHANOX 330) was assessed for the application of ethylene-propylene elastomers, EPDM, as high stabilized product in the radiation field. The

T. Zaharescu et al. / Journal of Advanced Research in Physics 1(1), 011012 (2010) where dose rate was 0.04 kGy/h. Cumulative irradiation (cycle: irradiation / measurement) was applied for each specimen in order to avoid any additional errors in the spectral evaluation. Dosimetry was carried out by Fricke dosimeter, which was freshly prepared. Specimens of about 4 mg were placed in aluminum tray for chemiluminescence investigation. The isothermal chemiluminescence (CL) measurements at proper temperatures (determined by the relative stability of samples) were carried out in LUMIPOL 3 (SAS, Slovakia). From the time dependencies of CL intensity two main kinetic parameters: oxidation induction period and oxidation rate on propagation stage were obtained according with the procedure reported earlier [17]. FTIR spectra were recorded on JASCO 4200A spectrophotometer at 50 scans and 4 cm-1 resolution. The hydroxyl index was evaluated from the ratio of absorbances at 3350 cm -1 and the invariant reference band (1376 cm-1) [18].
III.

improvement in the thermal and radiation stability is provided by hindered phenolic function, which efficiently interacts with free radicals formed from polymer macromolecules. The structural modifications are revealed by the change in IR spectra, which are sustained by the results obtained by means of mechanical testing and chemiluminescence. This qualification is carried out in real irradiation conditions for cables and O-rings placed outside of active zone of reactor. II. EXPERIMENTAL A. Materials The tested elastomers, commercially names KELTAN 8340A and KELTAN 5508 were provided by DSM Elastomers (The Netherland). Their main features are listed in Table 1. These ethylene-propylene terpolymers contain 2ethylidene norbornene as diene (the third component).
TABLE I MAIN CHARACTERISTICS OF STUDIED ELASTOMERS Polymer material Characteristics KELTAN 8340A KELTAN 5508 Ethylene content (%, w/w) 55 70 Diene content (%, w/w) 5.5 4.5 Mooney viscosity {ML (1+4) 80 70 1250C

RESULTS AND DISCUSSION

The phenolic antioxidants manufactured by CIBA GEIGY have trade names IRGANOX 1010 [pentaerythritol tetrakis(3 - (3,5-di-tert-butyl-4-hydroxyphenyl) propionate)] and ETHANOX 330 (1, 3, 5-trimethyl-2,4,6-tris (3,5-di-tertbutyl-4-hydroxybenzyl) benzene) that assures very high stabilization level at 2 % concentration relative to elastomers weight. Their structures are illustrated in Fig. 1. B. Sample preparation Plaques of 2 mm thickness were obtained by pressing in a proper electrically heated plate press for 10 minutes at 1800C after intimate mixing of elastomers with antioxidants. From these plaques dumbs were cut for mechanical testing. Some parts of them were used for chemiluminescence measurements after chopping. Films of 100-120 m of elastomers were pressed for spectral investigations. C. Irradiation and measurements Irradiation was performed in an irradiator, GAMMATOR M-38-2 installation (USA), provided with 137Cs source. Exposures were accomplished in air at dose rate of 0.4 kGy/h.
OH

Complex description on the interaction between high energy radiation and polymers can be found elsewhere [2, 19, 20]. The formation of free radicals by several scissions of weaker bonds creates intermediates for subsequent processes namely recombination, disproportionation or oxidation. Conditions under polymeric materials have to be investigated regarding the influence of these reaction rates. It is generally accepted that ethylene-propylene elastomers show significant resistance to the action of ionizing radiation [21-23]. Their radiochemical behavior is similar to polyethylene. On the opposite site, irradiation of polypropylene in air induces oxidation because of great proportion of tertiary carbon atoms. In fact, radiochemical oxidation starts with reaction between free radicals and molecular oxygen that exists or penetrates material by diffusion process. The extension of oxidation depends on the lifetime of radicals, the time of exposure and the temperature of radiolysis. General mechanism of polyolefin oxidation was proposed by Bolland and Gee [2] for thermal degradation of these polymers, but it is usually extended for high energy irradiated polyolefins. The main reactions occurred under irradiation are gathered in Fig. 2. Oxidative degradation can never be entirely eliminated because molecular oxygen is present in the majority of environmental conditions. Technological application of this class of polymers in the radiation processing field must take into account the consequences of oxygenated products accumulated during the start step of irradiation on material stability.
Initiation RH R. + H . Propagation R. + O 2 ROO . ROO. + RH ROOH + R. ROOH RO. + .OH 2 ROOH ROO. + RO. + H 2O Termination 2 R. R- R ROO . + R. ROOR . 2 ROO ROOOOR ROOOOR R'OH + R''R'''C=O + O 2

OH

H3C

CH2 CH3 CH2 CH3 OH

CH2

C CH2CH2COCH2 4 O

Transfer RO . + RH HO . + RH

HO

ROH + R. H 2O + R.

(a) (b) Fig. 1. Molecular structures of studied additives: (a) IRGANOX 1010 and (b) ETHANOX 330.

Fig. 2. Scheme on mechanism of radiation induced oxidation in polyolefins.

Similar alternative irradiations were performed with

60

Co,

The accumulation of oxidation products describes the evolution of progress in the stability of material. It may be

T. Zaharescu et al. / Journal of Advanced Research in Physics 1(1), 011012 (2010) depicted by the variation in the absorbances of characteristic functions, mainly carbonyl and hydroxyl groups. Because of the presence of di-octylphalate, the band at 1720 cm-1 was practically unavailable, presenting maximum absorbance from the beginning (Figs. 3a, 4a). The responses of the both materials in the neat state differ because the primary chemical structures are unlike (Table 1). The modifications induced in FTIR spectra over the first 50 kGy are not significant. The absorbance in the 3350 cm-1 band remained almost constant. This aspect is probably related on the low specific depositing energy. It means that in the case of nuclear power plants, outside the active area where dose rate is extreme low, the chemical transformations induced in time are not relevant.

behavior of samples is similar in the dose range up to 50 kGy. But by increase in the absorbed dose prominent accumulation on the spectral region of bonded hydroxyls can be noticed. The enhanced transferred energy onto the same mass unit causes an increase in the volume concentration of free radicals that leads to a faster accumulation of oxidation products. The presence of ETHANOX 330 in the composition of elastomers brings about a sustained stabilization (Figs. 3c, 4c). In addition, the inhibition of oxidation is assured by antioxidant, which does not allow further oxidation. Similar statement may be expressed for the studied ethylenepropylene terpolymers in the presence of the other studied antioxidant, IRGANOX 1010.

Fig. 3. FTIR spectra recorded on KELTAN 8340A (a) subjected to different 60Co-radiation doses (dose rate 0.04 kGy/h) 1. 0 kGy, 2. 4 kGy, 3. 14 kGy, 4. 50 kGy; (b) subjected to different 137Cs-radiation doses (dose rate 0.4 kGy/h) 1. 0 kGy, 2. 63 kGy, .3. 91 kGy; (c) in the presence of 2 % Ethanox 330 subjected to different -radiation doses (60Co, dose rate 0.04 kGy/h) 1. 0 kGy, 2. 4 kGy, 3. 14 kGy, 4. 50 kGy; (d) stabilized with the couple of additives (ETHANOX 330 and IRGANOX 1010) subjected to different -radiation doses (137Cs, dose rate 0.4 kGy/h) 1.0 kGy, 2. 63 kGy, .3. 91 kGy.

60

Fig. 4. FTIR spectra recorded on KELTAN 5508 (a) subjected to different Co-radiation doses (dose rate 0.04 kGy/h) 1. 0 kGy, 2. 4 kGy, 3. 14 kGy, 4. 50 kGy; (b) subjected to different 137Cs-radiation doses (dose rate 0.4 kGy/h) 1. 0 kGy, 2. 63 kGy, .3. 91 kGy; (c) in the presence of 2 % Ethanox 330 subjected to different -radiation doses (60Co, dose rate 0.04 kGy/h) 1. 0 kGy, 2. 4 kGy, 3. 14 kGy, 4. 50 kGy; (d) stabilized with the couple of additives (ETHANOX 330 and IRGANOX 1010) subjected to different radiation doses (137Cs, dose rate 0.4 kGy/h) 1.0 kGy, 2. 63 kGy, .3. 91 kGy.

The exposure of the same types of elastomers films to rays (137Cs), but under other dose rate (0.4 kGy/h) the

T. Zaharescu et al. / Journal of Advanced Research in Physics 1(1), 011012 (2010)

Fig. 5. CL intensity dependencies on degrading time for neat KELTAN 8340A subjected to various doses (dose rate 0.4 kGy/h). Temperature: 1700C; environment: air.() 0 kGy; () 7.2 kGy; () 14.2 kGy.

Fig. 7. CL intensity dependencies on degrading time for KELTAN 5508 in different stabilization states. Irradiation dose: 35 kGy; temperature: 2050C; environment: air. () pristine EPDM; () EPDM + IRGANOX 1010; () EPDM + ETHANOX 330.

Fig. 6. CL intensity dependencies on degrading time for nonirradiated KELTAN 5508 in different stabilization states. Temperature: 2200C; environment: air. () pristine EPDM; () EPDM + IRGANOX 1010; () EPDM + ETHANOX 330.

The coupling of these stabilizers induces an advanced inertness related to the propagation of oxidation in irradiated elastomers. Figs. 3d and 4d illustrate the constancy in the level of oxidation provided by hydroxyl band. The comparison between the irradiation effects presented in Figs. 3b, 3d, 4b and 4d reveals the advanced stability of materials due to the protection action of used additives. The susceptibility of polymers, namely ethylenepropylene elastomers is tightly related to the thermal strength of materials. The oxidation of polymer substrates is promoted by peroxyl radicals, which are formed as the result of the reactions involving molecular oxygen. The selfcatalyzed oxidative degradation is accelerated by the increase in free radical concentration. Fig. 5 depicts the differences that are pointed out between irradiated samples which received increasing irradiation energy. The scission of molecular backbones generates radicals that decay on the first 10 minutes from the start of heating (Fig. 5). The oxidation starts further, when sufficient amount of oxygen penetrates polymer bulk. The stabilization effect of added hindered phenols is evident (Fig. 6). Irradiation causes an acceleration of thermal degradation because of the existence of higher amount of reacting radicals. However, the scavenging action of antioxidants hinders the oxidative reactions of intermediates, which significantly reduces the rate of degradation (Fig. 7). The durability of materials under such high efficient protection becomes noteworthy. It is obvious that the items manufactured of ethylenepropylene terpolymers exhibit a very convenient resistance

Fig. 8. Chemiluminescence curves recorded for KELTAN 8340A highly stabilized with IRGANOX 1010 () and ETHANOX 330 ().

against their oxidation in high energy radiation field. Fig. 7 demonstrates that on 100 minutes of exposure, unprotected material is completely oxidized, while the same products modified with phenolic antioxidants (IRGANOX 1010 and ETHANOX 330) begin to be slightly oxidized. Moreover, after 400 minutes, samples stabilized with IRGANOX 1010 and ETHANOX 330 attend oxidation level of neat material corresponding to 20 minutes and 12 minutes, respectively. The slow increase observed in the chemiluminescence intensity of 35 kGy irradiated elastomers illustrates the benefits of antioxidant addition for the enlargement in the durability of products. At high temperatures the two antioxidants produce different effects in accordance with their protection activities. In Fig. 8 two chemiluminograms are presented, their evolution describing the induced effect on KELTAN 8340A irradiated at 14.8 kGy (dose rate 0.4 kGy/h). Table II lists the kinetic parameters calculated for unmodified materials. The lower content of propylene unit (55 %) in KELTAN 8340A determines a higher stability in comparison with similar compound, KELTAN 5508 (70 %), though the content of diene is somewhat the same. The low radiation stability of polypropylene is reported elsewhere [24]. The attack of oxygen takes place on tertiary carbons, which are the most vulnerable sites on the backbones of ethylene-propylene terpolymer. In Table II it must be also observed that testing temperature applied to KELTAN 5580 is higher that similar value for KELTAN 8340A due to the higher stability of initial material.

T. Zaharescu et al. / Journal of Advanced Research in Physics 1(1), 011012 (2010)

TABLE II KINETIC PARAMETERS COBTAINED FOR OXIDATION OF GAMMARADIOLYSED PRISTINE EPDM SAMPLES

Kinetic parameter

0 kGy

7.4 kGy
0

14.8 kGy

22.2 kGy

KELTAN 8340A (testing temperature: 170 C) Induction period 368 308 [min] Oxidation rate 2.21 2.26 [u.r./(g.min)]*105 KELTAN 5508 (testing temperature: 2200C) Induction period 21 17 [min] Oxidation rate 3.64 2.25 [u.r./(g.min)]*104

240 2.50

200 3.42

14 2.65

10 2.83

the long term application in the areas outside the active zones of nuclear power plants. The present results lead to the conclusion that KELTAN 5508 is more stable than Keltan 8340A, and ETHANOX 330 is more efficient than IRGANOX 1010 during the exposure of ethylene-propylene elastomers at low integral doses and dose rates. The concentration of 2 % in additive amounts is suitable for stabilization of synthetic elastomers destined to nuclear energy branch. This investigation is the first stage of a detailed research, which will goes on with the evaluation of life time of these products under high stabilization consistancy. The extension of this study will be focussed on the evaluation of life time of studied compositions. ACKNOWLEDGMENT This work was accomplished in the frame of INOVATION Program, project 235/2008, whose financial support was provided by AMCSIS. REFERENCES
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TABLE III KINETIC PARAMETERS OBTAINED FOR OXIDATION OF GAMMA-RADIOLYSED 0 STABILIZED EPDM SAMPLES. TEMPERTURE: 205 C Dose [kGy] Polymer material [min] 22.2 vox [u.r./(g.min)]*10
5

35.0 [min] 72 vox [u.r./(g.min)]*104

K8340A +Irgano 180 x 1010 K8340+ Ethanox 120 330 K5508 30 K5508 + Irganox 151 1010 K5508 + Ethanox 160 330 means oxidation induction replaces the word KELTAN

1.0

3.0 [2]

3.6 19.5 0.3 0.9

260 7 196 105

3.8 2.7 2.9 2.6 [3] [4] [5] [6] [7] [8]

time; vox denotes oxidation rate; letter K

Table III presents the kinetic characteristics obtained for stabilized systems. The results listed in this table are in a good agreement with other previous results obtained on neat and stabilized polyolefins with different molecular structures [25]. KELTAN 5508 presents the oxidation rate one order of magnitude less than KELTAN 8340A, that suggests the prominent option on it. The addition of hindered phenol antioxidants ensures long term stability by their reactions with hydrocarbon radicals formed during radiolysis. An experimental detail must draw attention: high testing temperatures. The experiments accomplished at other temperatures, for example 1900C provided similar results, i. e. lower oxidation rates on propagation stage and longer induction time, when materials keeps unchanged its functional features. It means that the operation at room temperature or much closed to it induces a much slower degradation, which can be converted into a high strength of material during the action of radiation and heat. IV. CONCLUSION This qualification is a serious option for optimal usage of materials under certain conditions. The tested antioxidants, IRGANOX 101 and ETHANOX 330, which efficiently block oxidation degradation in irradiated polymers ensure

[9]

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T. Zaharescu et al. / Journal of Advanced Research in Physics 1(1), 011012 (2010)

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