Article Excerpt

Traditionally, sulfur cure systems have been used to vulcanize many hose and belt compounds.
The heat resistance of sulfur cure systems can be improved by reducing or eliminating elemental
sulfur, which minimizes or eliminates polysulfide crosslinks and provides mainly mono- and di-
sulfide crosslinks. For maximum heat resistance, peroxides must be used because they provide
the most thermally stable carbon-carbon crosslinks.

Peroxides require special attention to the compounding additives. For example, antidegradant
selection is more restricted because many antioxidants interfere with peroxide crosslinking.
Furthermore, when using peroxides it is important to minimize acidic fillers to prevent cationic
decomposition of the peroxide which will result in a lower state of cure (lower hardness and
modulus with higher compression set). The addition of basic ingredients such as zinc oxide or
magnesium oxide, when possible, generally will increase peroxide crosslinking efficiency. Finally,
paraffinic oils are preferred, and the use of aromatic oils and solvents should be avoided.1

Cure systems and antidegradant packages are presented for the belt polymers polychloroprene
(CR), hydrogenated nitrile-butadiene copolymer (HNBR) and ethylene-propylene-diene polymers
(EPDM). Cure systems and antidegradant packages for specific hose applications will be
discussed.

Oxidation and antioxidants2,3

The properties of polymer vulcanizates will deteriorate when the material reacts with oxygen. As
little as 1-2 percent oxygen combined with the poly-mer seriously will degrade the properties of
the rubber vulcanizate. Any form of energy-heat, light or mechanical stress-can break polymer
bonds to start the oxidative process.

Antioxidants are materials that can interfere with any of the steps in the oxidation process. For
maximum effectiveness, a combination of two types of antioxidants-a radical trap and a peroxide
decomposer-requently can provide better protection against oxidative aging than either type of
antioxidant alone. Examples of primary or radical trap antioxidants are hindered amines i.e.
octylated diphenylamine (Octamine-brand, ODPA) and phenols i.e. butylated hydroxytoluene
(Naugard-brand BHT, BHT).

Secondary or peroxide decomposing antioxidants are exemplified by tris-nonylphenyl phosphite

(Polygard-brand, TNPP). The inclusion of a phosphite as a secondary antioxidant generally
provides improved color compared to the use of a phenol alone.

Antioxidants can be lost by physical means. If they are volatile, they may evaporate from the
rubber article during high temperature service. A comparison of the volatility of several amine
antioxidants at 177[degree sign]C is shown in Fig. 1. The alkylated phenyl-alpha-naphthylamine
(Naugard-brand PANA, PANA) is the most volatile of the amines in this comparison. The three
least volatile antioxidants are the N-phenyl-N'-(p-toluenesulfonyl)-p-phenyl-enediamine (Aranox-
brand, TPPD), 2,4,6-tris-(N-1,4-dimethylpentyl-p-phenylenedia-mino)-1,3,5-triazine (Durazone-
brand 37, TAPTD) and alpha-methylstyrenated diphenylamine (Naugard-brand 445, aMSDPA).
The aMSDPA is superior to its octylated (ODPA) and styrenated (Naugalube-brand 635, SDPA)
analogues for low volatility.

In rubber articles that will be immersed in a service fluid, the service fluid also may extract the
antioxidant out of the rubber article. Fig. 2 shows the relative solubility of several amine
antioxidants in heptane, which is a good model for modern-day hydrocarbon motor oils. The least
soluble antioxidants are Naugard 445-brand (aMSDPA), Naugard J (DPPD) and Naugard Q
(TMQ). These are more likely to remain in the rubber article and provide protection for longer
service time when immersed in hydrocarbons.

Ozonolysis and antiozonants2,4

Ozone is present in the atmosphere at minute levels, about 50 parts per billion (ppb, commonly
expressed as 5 parts per hundred million, pphm). Ozone typically is formed by the action of
sunlight on smog particles, so the level generally increases in summertime to 300 to 400 ppb,
levels which can be harmful to humans as well as rubber parts.

Ozone degradation can be observed as a surface discoloration, known as frosting. Frosting most
usually is encountered with the onset of summer. If the article is stretched while exposed, cracks
can develop and grow perpendicular to the applied strain. The prevention of ozone cracking is
important for a long useful life of the rubber article. Ozone has no effect under ordinary
circumstances on saturated polymers. Only diene-based polymers with main chain unsaturation
are attacked by ozone.

The typical ways to provide ozone resistance depend on forming a protective surface barrier
against ozone attack. The rubber compounder has several methods available to protect the
rubber part in service against ozone attack. As with many compounding approaches, there are
trade-offs involved.

Waxes of the appropriate molecular weight and structure will form a physical barrier at the rubber
surface. This provides a non-staining and non-discoloring approach to static ozone resistance.

Antiozonants based on para-phenylene diamines (PPDs) provide dynamic ozone resistance, but
they typically are discoloring and staining. The three main classes of PPD based antiozonants are
shown in Fig. 3.

For non-staining ozone resistance in a dynamic environment, Durazone-brand 37 (TAPTD) can

be used, and examples will be given.

PPD antiozonants

Diaryl PPDs are the least volatile type of PPD and, as indicated in Fig. 2, N,N'-diphenyl-para-
phenylene diamine (Naugard-brand J, DPPD) is comparable in volatility to typical antioxidants.

Alkyl/aryl PPDs can trap alkoxy radicals to provide additional functionality as an antioxidant. The
alkyl/aryl PPDs are the most popular type of staining antiozonant.

Dialkyl PPDs form tar-like oligomers that provide an impenetrable surface barrier against ozone
attack. Therefore, dialkyl PPDs can be used alone to provide ozone resistance. Diaryl and
alkyl/aryl PPDs require the use of a wax in order to provide ozone resistance. Dialkyl PPDs are
typically the most volatile of the staining antiozonants and reduce scorch times the most of the
PPDs.

Belt polymers

Polychloroprene (CR)

For many years, the standard V-belt polymer has been chloroprene copolymerized with sulfur.
These polymers can be cured with metal oxides alone, but the addition of an organic accelerator
such as a thiourea can speed up the rate of cure. The polysulfide linkages in the chloroprene-
sulfur copolymer limit the high-temperature resistance of the vulcanizate. With more aerodynamic
automotive styling, which restricts the size of the engine compartment, and increased engine
operating temperature for better fuel efficiency, the service limit of the chloroprene-sulfur
copolymer is being exceeded in many new automotive designs. Nevertheless, many V-belts
based on polychloroprene are in service.

The standard antioxidant for polychloroprene is octylated diphenylamine (Octamine-brand,

ODPA). Typically, ODPA and magnesium oxide are the first additives to be incorporated in the
mixing cycle.5 ODPA also provides an improvement in ozone resistance, see Table II.6

Table II shows that alkyl/aryl PPDs, as exemplified by N-isopropyl-N'-phenyl-para-

phenylenediamine (Flexzone-brand 3C, IPPD), are scorchy and provide poor bin storage stability.
The least scorchy type of PPD for use in polychloroprene is a diaryl such Novazone-brand AS
(DAPD). For non-staining ozone resistance, Durazone-brand 37 (TAPTD) can be used. An
example is shown in Table III.7 Whereas the Novazone AS compound turns brown from the
blooming of this diaryl PPD, both the Durazone 37 and Octamine compounds remain black.

For maximum ozone resistance, a combination of wax and PPD provides the results, see Fig. 4.8
Properly compounded, polychloroprene is serviceable to 120[degree sign]C.9

Hydrogenated nitrile-butadiene (HNBR)

HNBR polymers possess excellent heat and oil resistance and can be compounded for good flex
fatigue. It is the dominant polymer for synchronous belts in Japan and is gaining use in Europe,
according to Hashimoto and co-workers.10 The selection of the cure system involves a trade-off
between heat aging and flex fatigue. Peroxides provide the best heat resistance, but low sulfur or
sulfurless cures generally have better flex fatigue. The work of Upadhyay11 in this area is shown
in Fig. 5. With peroxide crosslinking that also polymerizes zinc diacrylate to form an in-situ filler,
Brown12 reports that HNBR can provide excellent toughness and high dynamic modulus at
elevated temperature.

As is typical of peroxide cures in many polymers, the selection of the antioxidant system in HNBR
is important for optimum high-temperature performance. Generally, a combination of a Naugard
445 (aMSDPA) with an antioxidant synergist such as zinc 2-mercaptotoluimidazole (ZMTI) is
recommended. Work in the Uniroyal Chemical laboratory has shown that the synergist alone
provides relatively poor high-temperature aging. Furthermore, the ratio of synergist to Naugard
445 is less important than the total level of antioxidant. As the more economical component,
higher levels of Naugard 445 can be used to provide better aging of HNBR at 175[degree sign]C.
Selected data is shown in Table IV.13

In some belting applications, the full heat resistance potential of HNBR may not be required. In
this case, the higher cost of HNBR may be partially offset by blending with a millable urethane.
Selected data is shown in Table V.14 Generally, about 30 percent millable urethane can be
added to HNBR without significant deterioration in properties.

Ethylene-propylene-diene (EPDM)

It has been determined that, in several belt applications, casual oil and grease contact does not
cause belt failure. This allows the use of hydrocarbon polymers such as EPDM as a material of
construction for belts. In addition to being relatively economical, EPDM...