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ABSTRACT: In this study, conifer wood our was evalu- predominant, increase in a compliance with the increase of
ated as a ller to NBR or NBR/PVC compounds studying it Mmax and DM when the lling level increases. The depen-
inuence on their cure characteristics and mechanical prop- dence is other when NBR and PVC are in equal amounts or
erties. It was shown that the lling by wood our offers a PVC predominates. As a most probable explanation of the
possibility to obtain high modulus high elastic or less elastic effect of the wood our on the cure characteristics is ac-
or rigid wood like vulcanizates by varying of both the lling cepted, the inuence of the wood our polar groups as well
level and NBR/PVC mass ratio.It was established that in as of the presenting as wood our humidity water mole-
contrary to the mineral llers usually causing signicant cules, the specic mechanical properties of the wood our-
delay of the vulcanization process, the wood our shows a lled NBR or NBR/PVC compounds could be connected (to
tendency to reduce the optimum cure time, 90. Modulus some extend) with a specic interface interaction between
M100 and Shore hardness of the wood our-lled vulcani- the wood our particles and the polymer matrix. 2003
zates of NBR or NBR/PVC compounds in which NBR is Wiley Periodicals, Inc. J Appl Polym Sci 90: 2734 2739, 2003
EXPERIMENTAL
Nitrile butadiene rubber (NBR 40, manufactured in tion was carried out at this same temperature and the
Russia, with parameters according to Russian stan- optimum cure time.
dard GOST 7738/79), Polyvinylchloride (PVC-S 64, The mechanical parameters were determined ac-
manufactured by Devnya Chemical Combine, Bul- cording to ISO/R37 and the heat agingaccording to
garia, with parameters according to Bulgarian stan- ISO/188.
dard 8806-71) and conifer wood our (manufactured The water adsorption was measured using 50 50
by Firm Maritsa, Kostenets, Bulgaria, with parame- 2-mm samples kept in distilled water for 24 h. The
ters according to Bulgarian standard 3718-74, with corresponding calculations were performed to the fol-
particle sizes of 60 100 mm and a humidity of 6%) lowing formula:
were used in this study. The model NBR compounds
contain traditional ingredients (phr): NBR-40, 100; W a P 1 P 0 100/P 0 , %
wood ourvaried; stearic acid, 2; zinc oxide, 3; sul-
phur, 2; sulphenamide accelerator (Vulkacit CZ, where Wa is the the water adsorption, P0 is the the
Bayer), 2. The model NBR/PVC compounds contain weight of the sample before testing, and P1 is the
the same ingredients in the same amounts but calcu- weight of the sample after keeping it in water.
lated to 100 phr NBR excluding the wood our. The The IR spectrum of the conifer wood our was
variables, wood our amount and NBR/PVC mass taken down from a KBr tablet with a Perkin-Elmer
ratio, are shown in Tables I and II. All the materials FTIR Spectrometer 1600.
used were of standard rubber industry grade and not
puried for this study.
RESULTS AND DISCUSSION
NBR/PVC mass ratio was varied in a way giving
one of each type of the compounds: (1) with a pre- The visual observation of the mixing process showed
dominant amount of NBR, NBR/PVC 80/20 phr, (2) an excellent wood our intake and homogenization of
with equal amounts of NBR and PVC NBR/PVC the NBR and NBR/PVC compounds as well as a pos-
50/50 phr, and (3) with a predominant amount of sibility for a relatively high degree of lling up to
PVC, NBR/PVC 40/60. 90 100 phr even in the absence of any process aid for
The model mixtures were prepared on laboratory a large volume of ller incorporation. The wood our
roll mill with a friction ratio of 1 : 1.4 in a conventional disperses very uniformly in the polymer matrix (NBR
way. The wood our was added at the rst prepara- or NBR/PVC mixture), independent on the lling
tion stage and PVC before all other ingredients. level, as it was demonstrated by our microscopy ob-
The microscope photographs are taken down from servation (Fig. 1). The detailed electron microscope
nonvulcanized samples in polarized light using a photographs (Fig. 2) showed that the wood our par-
MBI-6 microscope. The electron photomicrographs are ticles incorporated in the polymer matrix are not as-
taken down from carbon replica of the fragile fracture sociated (maybe due to their specic branched shape),
surface of the corresponding vulvanisate using a Phil- and they are very well wetted by the matrix polymer.
ips EM 400 apparatus. The last one conrms by the relatively low water
The vulcanization characteristics were determined adsorption of all wood our lled compounds (it does
according to Bulgarian standard 15754-83 with a Mon- not surpass 9.3 wt % in all cases) and its similarity to
santo Rheometer MDR 2000 at 160C. The vulcaniza- that of the corresponding control nonlled com-
pounds (up to about 8 wt %) (Tables VIII and IX). The
processability of the wood our lled compounds is
TABLE I comparable to that of the carbon black-lled one. For
NBR Compounds with A different example, the processability coefcient, , and the ho-
Wood Flour (WF) Levels mogenation time, t (estimated from Brabender plasto-
Mix no. 1 2 3 4 5 grams) of the model NBR compounds lled with 35
phr conifer wood our or 35 phr carbon black, FEF are
WF, phr 0 35 50 70 90
respectively: 0.27 or 0.29, and t (min : s)2 : 50 or
2736 VLADKOVA, VASSILEVA, AND NATOV
TABLE V
Mechanical Parametrs of NBR Vulcanizates
with Different Wood Flour (WF) Levels
Mix WF, M100, , , Hardness
no. phr MPa MPa % shore A
TABLE IV
Cure Characteristics of NBR/PVC Compounds of Different NBR/PVC Ratios and Wood Flour (WF) Levels
Mix NBR/PVC, Mmin, Mmax, M, ts1, t90, Vc,
no. mass ratio WF, phr dNm dNm dNm min:sec min:sec % min1
CONCLUSIONS 5. Alma, M. H.; Maldas, D.; Shiraishi, N. J Polym Eng 1998, 18, 161.
6. Alma, M. H.; Shiraishi, N. J Polym Eng 1998, 18, 179.
The lling of NBR or NBR/PVC compounds by wood 7. Alma, M.; Kelley, S. J Polym Eng 2000, 20, 365.
our offers a possibility to obtain high modulus high 8. U.S. Pat. No 4594372/10.06.86.
elastic or less elastic or rigid wood-like vulcanizates 9. Eur. Pat. No 953/16.12.86.
10. Bulgarian Pat. No 42763/10.10.86.
by varying both the lling level and NBR/PVC mass
11. Bulgarian Pat. No 43226/6.01.87.
ratio. 12. Gauthier, R.; Joly, C.; Coupas, A. C.; Gauthier, H.; Escoubes, M.
The cure characteristics of the wood our-lled Polym Comp 1998, 19, 287.
NBR or NBR/PVC compounds indicate that, in con- 13. Georgiev, V. PhDl Thesis, Univ. for Chemical Technology and
tradiction to the mineral llers, usually causing signif- Metallurgy, Soa, 1988.
icant delay of the vulcanization process, the wood 14. Xavier, S. F.; Schultz, J. M.; Friedrich, K. J Mater Sci 1990, 25, 241.
15. Wang, Y.; Huang, H. S. J Appl Polym Sci 1996, 60, 1779.
our demonstrates a tendency to accelerate it. The
16. Xanths, M. Plast Rubber Process Appl 1983, 3, 223.
effect of the wood our on the cure characteristics is 17. Myers, G. E.; Chahyadi, I. S.; Gonzales, C.; Goberly, C. A.;
explained with the inuence of the wood our polar Ermer, D. S. Int J Polym Mater 1991, 15, 171.
groups and the presence of water molecules as a wood 18. Kokta, B. V.; Raj, R. J.; Daneault, C. Polym Plast Technol Eng
our humidity. 1989, 38, 3.
The mechanical parameters, modulus M100 and 19. Nagay, N.; Erman, B. Hybrid Reiforcement in Nitrile Rubber
Compounds; Proc Int Symp EUROFILLERS 99, Sept. 6 9,
Shore hardness and the water adsorption of both NBR
1999.
or NBR/PVC compounds increase, whereas the ten- 20. German Pat. No 3345858/1985.
sile strength and elongation at break decrease with the 21. Anmova, E. A.; Likin, A. S. Kauchuk Rezina, 1984, N 11, 39.
increase of the lling level. The simultaneous decrease 22. Dogadkin, B.; Dontsov, A.; Shershnev, B. A. Chimiya Elas-
of the tensile strength and elongation at break gave us tomerov; Chimiya: Moskow, 1981.
reason to ascribe the nonmodied conifer wood our 23. Klemm, D. Comprehensive Cellulose Chemistry; Wiley-VCH,
New York, 1998.
to the inert rubber llers.
24. Raimo, A., Ed. Analitical Methods in Wood Chemistry, Pulping
and Papermaking; 1999, p. 316, XIII.
References 25. Dechant, J.; Danz, R.; Kimmer, W.; Schmolke, R. Ultrarotspe-
ktroskopische Untersuchungen an Polymeren; Akademie Ver-
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p. 1. 26. Bridson, A. The Chemistry of Rubber; Applied Science: London,
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Technol 1996, 30, 39. 27. Blokh, G. A. Organicheskie Uskoritely Vulcanizatsii Kau-
3. Alma, M. H.; Yoshioka, M.; Yao, Y.; Shiraishi, N. Holzforschung chukov; Chimiya: Leningrad, 1972.
1996, 50, 85. 28. Ivanov, M. Doctoral Thesis, UCTM, Soa, 1997.
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