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PUBLISHED ON MAY 19, 2008 @ 6:00AM EST

Hydrogenated nitrile for oil eld applications

By John E. Dato, E.C. Campomizzi and D. Achten

In fundamental terms, fully hydrogenated HNBR can be described as a copolymer consisting of randomly distributed sequences of ethylene and
acrylonitrile monomers.

The intrinsic combination of good heat, extreme oil and chemical resistance, coupled with outstanding physical properties and ease of processing for
HNBR, can be attributed to its composition and structural arrangement.

The use of HNBR for rubber articles such as stators (drilling motors and progressive cavity pumps), packers, blow out preventors and drill bit seals, can
extend the lifetime of the articles thereby reducing the maintenance frequency or extending the replacement cycles for those parts.

This benefit can potentially translate into substantial operational cost savings without compromise to safety.

Furthermore, advances in technology have permitted the development of new grades. New low viscosity polymers based on Therban AT (Advanced
Technology) provide polymers which can be processed as easily as regular nitrile polymers (NBR) while retaining the advantageous properties of
HNBR.

Other developments in carboxylate technology have allowed development of Therban XT (HXNBR) which offers the advantages of carboxylated NBR
but with the improvements in heat resistance and abrasion (caused by the reduced stiffness of the polymer backbone) afforded by the hydrogenation of
the polymer backbone.

By utilizing the new HNBR polymers, unprecedented latitude of compounding as well as novel ways of processing can be attained. This in turn opens
the door for new dimensions of design. Examples will be given in the paper.

Discussion

The development of new elastomers with improved performance profiles has become increasingly important, particularly for rubber parts used in the oil
industry.

New demanding methodologies have emerged such as horizontal drilling and smart well techniques in combination with increasingly adverse conditions
of deeper wells and higher temperatures. The more extensive use of corrosion inhibitors to protect production equipment from unpredictable mixtures of
hydrocarbons, possibly containing sulfur, H2S, CO2, CH4, and the extensive use of steam and brine injections to improve yields from even the smallest
oil pockets have raised demands on standard elastomers to an extent that they are reaching their performance limits.

Consequently equipment containing seals, stators, packers and other parts must be maintained or replaced more frequently leading to increased cost
with respect to both parts and to operational down-time. It is readily apparent that reliability and durability of equipment becomes a limiting factor for the
total output and overall return for each drilling operation.

A number of limiting performance criteria for several rubber parts used in the oil well services industry have been identified. These are:

*Resistance to high temperature and to aging.

*Resistance to swelling by aggressive fluids and gases.

*Resistance to explosive decompression.

*Mechanical properties and resistance to deformation at elevated temperatures.

*Abrasion and wear resistance under extremely adverse conditions.

*Processing properties to allow a greater freedom of compounding and new part design and production techniques.

It is well known that Therban HNBR is an oil resistant polymer that is well suited to deliver the performance criteria needed by the oil well sector. This
outstanding property profile is attributable to the saturated polymer backbone in combination with the highly polar and inert acrylonitrile functional group.
Starting from NBR—still the workhorse polymer for the oil industry—HNBR has a similar oil resistance as NBR but with significantly improved chemical
and heat resistance as well as improved physical properties over a wide temperature range.

Through the hydrogenation process, the double bonds of NBR are eliminated, the typical sites susceptible to chemical and oxidative attack. At the same
time the irregularly placed butadiene units are transformed into polyethylene sequences, giving HNBR its ability to reversibly crystallize under strain
resulting in physical properties comparable to natural rubber.

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Hence, the selective hydrogenation of the double bonds in acrylonitrile-butadiene rubber produces a specialty elastomer, hydrogenated acrylonitrile-
butadiene rubber which may be formulated to produce a material conveying an excellent balance of properties, including mechanical and dynamic as
well as improved resistance to hot air, oils, chemicals and abrasion.

Therban is characterized by a combination of properties that make rubber goods resistant to service conditions found in oil exploration and production
environments.

Typical vulcanizate properties for HNBR are shown in Table 1. Appropriate compounding techniques and selection of the most suitable Therban
polymer enable the properties of the vulcanizates to be adapted to specific requirements.

Therban vulcanizates also exhibit good resistance to alkaline solutions and dilute acids. The resistance to a caustic soda solution (25 percent) at 100°C
and to a dilute hydrochloric acid solution (18 percent) at 50°C is very good. Generally the chemical and oxidative stability improve with increasing
degree of hydrogenation.

Stability under oilfield conditions

Rubber articles for oilfield application must withstand both mechanical wear and chemical attack by drilling mud and other aggressive fluids. Depending
on the actual well conditions, the parts may be exposed to mixtures of oil with acids and amines, as well as hydrogen sulfide, methane and carbon
dioxide. In addition, high pressure and temperature conditions are encountered, especially as the well depth increases.

Resistance to hydrogen sulfide and corrosion inhibitors

Hydrogen sulfide, which occurs in crude oil and natural gas wells, is an aggressive media encountered with increasing frequency. Other substances
found in the service environment that tend to aggressively attack rubber articles include amine corrosion inhibitors, carbon dioxide and acids.

For the test results described below, use was made of mixtures consisting of diesel oil, sour gas, water, and amine-based corrosion inhibitors NACE A
and NACE B. Fig. 2 shows that the retention of tensile strength of HNBR based compound is superior to that of standard FKM, NBR and XNBR when
aged at 150°C in a mixture consisting of diesel oil, sour gas and water.

Similarly, good retention of tensile strength for HNBR is observed when the corrosion inhibitors NACE A (Fig. 3) and NACE B (Fig. 4) are added to the
mixtures. In these cases the properties of HNBR remain substantially unchanged, whereas those of FKM, NBR and XNBR suffer significant reduction in
tensile strength. For the compounds based on these polymers, the tensile at break after aging is in the range of 7 to 8 MPa representing a loss in
tensile in the 50-80 percent range.

On the other hand, the tensile at break for the HNBR-based compound is still in the order of about 18 MPa, representing a loss in tensile of about 30
percent. Results obtained with the oil soluble NACE B show the same behavior as observed when water-soluble NACE A is used.

In the described tests Therban elastomer was compared with FKM, NBR and XNBR, all of which are known to withstand heat and/or oil swells.
Commercially available elastomers were chosen for the tests. In the case of FKM, a bisphenol crosslinked compound was used.

To improve properties wherever swelling and aging in crude oil is a problem the use of fully hydrogenated high ACN content HNBR such as Therban A
4307 is strongly recommended.

Resistance to explosive

decompression

Rubber articles used in the oil industry are also exposed to extremely high pressures.

At these extreme pressure conditions, low-molecular weight hydrocarbons as well as other gases, such as carbon dioxide and hydrogen sulfide, are
considerably more soluble in the rubber article than is the case at normal pressures. Diffusion of the gases into the article occurs until equilibrium is
established.

At a sudden pressure drop, as might result through a sudden change in the operating conditions, the dissolved gases tend to escape rapidly from the
rubber causing internal destruction of the part. The resistance to this ``explosive decompression'' is polymer and compound dependent.

Fig. 5 shows that vulcanizates based on HNBR elastomers are highly resistant to explosive decompression. Dry carbon dioxide at 5.2 MPa (750 psi)
was used in the test to evaluate explosive decompression resistance. The carbon dioxide gas was introduced into the pressure vessel containing the
test specimens.

Exposure time was 24 hours at room temperature, after which the specimens were explosively decompressed by opening an exhaust valve, allowing
the pressure to drop from 5.2 MPa to atmospheric pressure in less than 10 seconds.

The criteria used to rank the compound performance under these test conditions were resistance to blistering and destruction, as well as retention of
physical properties, including tensile strength at break, elongation at break, and hardness change.

Fig. 6 shows the effect of explosive decompression testing on tensile strength. The specimens were aged as described (after aging in CO2 at 23°C, 5.2
MPa for 24 hours) and then were tested one hour after the decompression step. These results showed an even greater differentiation among the
polymers tested.

It is generally recognized that explosive decompression is improved by the following:

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*the solubility of gases in the polymer is low (high ACN content is recommended)

*the polymer should have high impermeability to gases (high filler loading)

*the physical properties are as high as possible (high tear resistance, tensile strength)

For most elastomers, permeability and solubility can be adjusted by means of compounding techniques. Highly filled compounds lead to better results in
explosive decompression tests than lightly filled compounds.

Advanced Technology Therban AT

In order to meet performance requirements, compounds for many oilfield applications are formulated to high durometer using high levels of fillers. The
need for high filler levels often results in high compound viscosities which are contrary to good processing requirements/needs.

Typically these problems are overcome by the introduction of plasticizers and process aids. However, these additives are often detrimental to product
performance because plasticizers can be extracted and exchanged by media, and they influence permeation and solubility of gases.

The most recent breakthrough in HNBR technology has been the development of a new class of low viscosity HNBR products by Lanxess now
available commercially as Therban AT. Previously, ultra low viscosity HNBR polymers were impossible to manufacture because of limitations in the
available viscosity for NBR feedstocks.

Compared with conventional HNBR products having a raw polymer Mooney in the nominal range of 65, these new Therban AT products have a typical
raw polymer Mooney of 39. They are available in a wide range of ACN and RDB levels, as shown in Table 2. These products have clearly demonstrated
the following advantages over regular viscosity HNBR grades:

Low molecular weight (low viscosity) provides improved processability: faster mixing (shorter black incorporation times); significantly better flow and
faster mold filling (shorter cycle times); improved extrusion rates and extrudates having smoother surfaces and sharper edges.

Narrower molecular weight distribution helps to maintain excellent physical strength properties despite drop in molecular weight.

Elimination or reduction of plasticizer is possible to improve heat aging, compression set, physical properties and adhesion.

Processability can be maintained at higher filler loadings, thereby enabling an extended hardness range and providing cost savings potential through
higher compound extension.

The advantages in processing properties for Therban AT are illustrated in Fig. 7. Compared with standard HNBR, Therban AT shows lower viscosity
levels through the entire range of shear rates typically encountered in rubber processing.

Fig. 8 compares a standard HNBR with Therban AT, both containing 34 percent ACN, 0.9 percent RDB. Therban AT has a significantly lower raw
polymer viscosity compared with standard HNBR. This translates to a significantly lower compound viscosity as well.

Comparison of vulcanizate

properties for Therban AT

A study was conducted to compare various compound and vulcanizate properties for standard HNBR and Therban AT. Both polymers contain 34
percent ACN, 0.9 percent RDB.

The results shown in Table III and Fig. 9 demonstrate that at a constant loading of N-330 carbon black, Therban AT provides a dramatic reduction in
compound viscosity. Modulus, hardness and compression set of Therban AT can be easily adjusted by a minor variation in either filler loading or
peroxide level to reach the same or even better performances than standard HNBR without losing the advantage of easier processing.

The key benefits for using new Therban AT are summarized in Fig. 10.

Therban AT can be utilized in numerous oilfield applications. A list of potential applications and benefits is summarized in Fig. 11.

Carboxylated Technology Therban XT

Hydrogenated carboxylated acrylonitrile-butadiene (HXNBR) provides vulcanizates possessing outstanding mechanical properties (tensile, elongation
and tear) combined with excellent property retention at high temperatures.

In addition, the vulcanizates exhibit excellent abrasion resistance, adhesive strength as well as improved hot air aging resistance over carboxylated
nitrile. In severe oilfield environments HXNBR is recommended for numerous applications including drill bit seals, ram packers, pipe wipers and seals
requiring enhanced metal adhesion.

Lanxess produces a commercial HXNBR polymer identified as Therban XT VP KA 8889. It contains 34 percent acrylonitrile, 5 percent carboxylic acid
groups and 3.5 percent residual double bond content. The structure of HXNBR is illustrated in Fig. 12.

Hydrogenation of carboxylated nitrile to produce HXNBR achieves the following vulcanizate improvements:

*Mechanical properties (tensile strength and elongation) from 23°C to elevated temperatures (170°C)

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*Tear resistance from 23°C to 170°C

*Pico abrasion resistance

*Adhesive strength to substrates such as nylon at 125°C

*Hot air oxidation resistance

HXNBR can be formulated alone or in blends with HNBR to target ranges within this set of outstanding properties.

Resistance to abrasion

Resistance to mechanical wear is another basic requirement for elastomer parts used in the oil industry. HNBR is recognized to be superior to most
other elastomers.

It is capable of providing long-term service at high temperatures up to 165°C and short term service up to 185°C. If severe wear is the main reason for
failure of parts the use of Therban XT, a new HNBR grade containing 5 percent carboxyl groups, is recommended.

To further boost physical properties, Therban XT can be combined with zinc diacrylate. Blends containing ZDA (available under the brand Therban ART
can achieve a unique combination of physical properties—tensile strengths of 40 MPa, 200 percent elongation at break, DIN abrasion values

Fig. 13 compares some basic physical properties that can be achieved using standard HNBR, Therban XT, and Therban XT in combination with ZDA.
Therban XT provides high hardness and modulus, high tear resistance, and high abrasion resistance. This combination of properties is useful in various
oilfield applications, including drill bit seals, ram packers and pipe wipers.

Resistance to oilfield fluids

It has been shown that Therban XT can provide a unique combination of vulcanizate properties for oilfield components. However it is also important to
consider the performance of HXNBR in various aqueous fluids.

For example, it is generally recognized that XNBR, due to its carboxyl functionality, exhibits higher water swell than NBR.

A study was conducted to assess the swell characteristics of Therban XT compared with other typical oilfield polymers. The other polymers included
standard NBR, low-water-swell NBR, standard HNBR, and FKM.

In addition Therban XT was evaluated in various blend ratios with standard HNBR and also in a blend with Therban ART. For this study, both carbon
black and silica fillers were evaluated. The formulations used for the design study are shown in Table IV.

Stress-strain properties were assessed for each of the compounds. Results are shown in Fig. 14. All compounds were designed to achieve a similar
hardness range. All of the NBR and HNBR formulas show very high tensile strengths (greater than or equal to 20 MPa) compared with the FKM formula
(12 MPa).

All vulcanizates were immersed in distilled water at 100°C for periods of 70, 168 and 504 hours. The values for volume swell in distilled water are
shown in Fig. 15.

All of the HNBR and HXNBR vulcanizates show very low volume changes. They provide water swell values that are equivalent to, or better than, the
NBR vulcanizates. The fumed silica filler shows particularly low water swell. The FKM vulcanizate shows very high volume change after 504 hours
aging.

All vulcanizates were immersed in a solution of 2 percent calcium chloride and distilled water to simulate brine environments encountered in oilfield
applications. The vulcanizates were aged at 100°C for periods of 70, 168 and 504 hours.

The values for volume swell in calcium chloride are shown in Fig. 16. All of the HNBR and HXNBR vulcanizates show low volume changes, comparable
to standard and low-water-swell NBR. The FKM vulcanizate shows particularly high swell after aging 504 hours in calcium chloride solution compared
with HNBR.

Since NBR is still considered to be the workhorse polymer for the oil industry, it can be concluded that HNBR and particularly Therban XT are both
viable alternatives for high temperature environments requiring excellent resistance to water and brine media.

In order to assess the effect of oil swell, HNBR and FKM vulcanizates were immersed in IRM 903 at 150°C for a period of 70 hours. The NBR
vulcanizates were not tested at 150°C. The values for volume swell in IRM 903 are shown in Fig. 17.

HXNBR shows slightly lower volume change than standard HNBR, even though the ACN contents are about 33 and 36 percent respectively. The lower
volume change for HXNBR is indicative of the higher crosslink density and higher modulus which is achieved via ionic crosslinking with HXNBR.

As expected, the volume changes for blends of HXNBR and standard HNBR show intermediate values. Among the polymers tested, the volume change
is lowest with FKM; however, it should be noted no HNBR polymers with high ACN content were tested in this series. The oil swell for HXNBR can be
further improved by blending with an HNBR containing 43 percent ACN content.

To assess wear characteristics, the NBR, HNBR, HXNBR and FKM vulcanizates were tested for Pico abrasion. The values for abrasive index are
shown in Fig. 18. A high abrasive index translates to low abrasion volume loss. All of the vulcanizates which contain HNBR clearly show superior

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abrasion resistance compared with NBR and FKM.

On top of that, for example, the compound containing only 35 phr of HXNBR even shows a two-fold improvement in abrasion resistance compared to
standard HNBR. The sample containing HXNBR and Therban ART shows the highest abrasion resistance of all samples tested.

From the results of this compounding study, it can be concluded that Therban XT provides high physical properties, low volume change in water and
brine, low volume change in IRM 903 oil, and excellent Pico abrasion resistance. Abrasion can be further enhanced by using blends with Therban ART.
Some of the key properties, and potential oilfield applications, for HXNBR are summarized in Fig. 19.

Some of the key properties for HNBR are summarized in Fig. 20.

This paper has illustrated some of the many benefits that can be achieved by using HNBR elastomers. In addition to its good heat, oil, fuel and
chemical resistance, Therban provides a good combination of mechanical properties, tear strength and abrasion resistance.

Therban with its new, low viscosity AT line, its carboxylated Therban XT and its Zinc-Diacrylate reinforced Therban ART specifically addresses the
needs of state-of-the-art oilfield technologies and demanding production methods that have to meet increasingly severe conditions and adverse
environments. Some typical applications of the wide variety of oilfield components in which the Therban product range can be used are listed in Fig. 21.

Conclusions

The development of new elastomers with improved performance profiles has become increasingly important, particularly for rubber parts used in the oil
industry. New demanding methodologies have emerged such as horizontal drilling and smart well techniques in combination with increasingly adverse
conditions of deeper wells and higher temperatures.

The more extensive use of corrosion inhibitors to protect production equipment from unpredictable mixtures of hydrocarbons, possibly containing sulfur,
H2S, CO2, CH4, and the extensive use of steam and brine injections to improve yields from even the smallest oil pockets have raised demands on
standard elastomers to an extent that they are reaching their performance limits.

The use of HNBR for oilfield components can extend the lifetime of the articles thereby reducing the maintenance frequency or extending the
replacement cycles for those parts. These benefits translate into substantial operational cost savings without compromise to safety.

Advances in polymer technology have enabled the introduction of new grades specifically addressing the needs of the oil-well industry. New low
viscosity polymers based on Therban AT (Advanced Technology) provide polymers which can be processed as easily as regular nitrile polymers while
retaining or even improving the advantageous properties of HNBR.

Advances in Carboxylate Technology have enabled the development of Therban XT which offers the advantages of carboxylated NBR but with the
improvements in heat resistance afforded by the hydrogenation of the polymer backbone. ZDA-modified HNBR's (Therban ART provide excellent
resistance to mechanical wear.

By utilizing these new HNBR polymers, unprecedented latitude of compounding as well as novel ways of processing can be attained. This presentation
has illustrated the performance profile and property improvements for new Therban polymers in various oilfield components.

Typical application examples have been recommended.

Acknowledgements

The authors wish to thank the management of Lanxess Corp. for support and permission to present this work. Acknowledgment should also be given to
Lanxess Technology Support Services, as well as numerous other individuals whose work contributed to the generation of data used in this
presentation.

References

1. J. Mirza, F. Leibrandt, J. Thoemer, Bayer Corp. Internal Paper No. 726, May 26-29, 1987, ``Hydrogenated Nitrile Rubber for Improved Durability of
Rubber Parts in Automotive and Oil Field Applications.''

2. J.J. Ridland, J.R. Moore, presented at Energy Rubber Group Technical Meeting, 1991, ``Evaluation of HNBR in Severe Oilfield Environments.''

3. J.J. Ridland, J.R. Moore, Paper No. 871, presented at Rubbercon, 1992, Brighton, England, ``Optimization of HNBR for Explosive Decompression
Service.''

4. J. Thoermer, J. Mizra, N. Schoen, Elastomerics, 1986.

5. J.J. Ridland, J.R. Moore, ``HNBR for Oilfield Applications,'' presented at PRI Conference, England, 1990.

6. TN 285 Bayer internal communications, 1991.

7. F. Guerin, S.X. Guo, ``Improving the Processability of HNBR,'' ACS 2004 fall meeting.

8. D. Achten, L. Leutewiler, F. Encinas, S. Baba, ``A whole new family of HNBR grades improving your freedom in compounding and part design,''
Brazilian Rubber Congress, 2005.

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9. S.X. Guo, F. Guerin, ASC Paper No. 62, 2004.

10. R. Parg, C. Wrana, D. Achten, Kautsch. Gummi Kunstst. 58 (3) 2005, 109.

11. C. Wrana, D. Achten, C. Ong, Lanxess Deutschland GmbH ``Influence of Polymer Viscosity on Mechanical and Dynamic Mechanical Properties of
Hydrogenated Nitrile Rubber,'' German Rubber Conference Nuremberg, 2006.

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