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NEW POSSIBILITIES FOR SILANE PE-X MATERIALS

USING A NOVEL CROSSLINKING CATALYST SYSTEM


AND INNOVATIVE PE RESINS

Magnus Palmlöf, Borealis AB


Carlo Quaretta, Giacomini

ABSTRACT

Silane crosslinking is one of the major methods used commercially today to bring about
crosslinking of pipes. However, to achieve reasonable crosslinking rates it is necessary to add
a catalyst masterbatch at extrusion. In addition some kind of post extrusion treatment at
elevated temperature is necessary. Catalyst systems used in the pipe industry have all been
based on tin, usually di-butyl-tin-di-laurate (DBTL). The tin catalyst and the post extrusion
treatment enable the pipe to achieve the 65% degree of crosslinking required by the
specification within a few hours for a standard plumbing pipe. This should be compared to
several months needed to crosslink at ambient conditions. There are however some drawbacks
connected with the post treatment of the pipes, e.g. cost for the handling of an extra
production step, investment in equipment and space for hosting the equipment. A new catalyst
system (Ambicat) for silane PE-X pipe manufacturing was recently launched on the market.
By using this novel technology there are possibilities to avoid the previously mentioned
drawbacks. This technology allows desired crosslinking to take place within a week at
ambient conditions. In combination with new innovative base graft materials very flexible
piping can be produced and still meet the ISO/CEN and DIN standards for HDPE-X. It is
foreseen that this material/catalyst concept would be particularly attractive for plumbing and
heating pipes, a variety of multilayer pipes and novel pipeline renovation solutions. A short
overview on new high strength silane materials is also given.

INTRODUCTION

The introduction of crosslinked polyethylene (PE-X) for pipe applications started in 1972
with the under floor heating of the sports arena in Munich as a snow and ice melting system,
built for the Olympic Games. Since then PE-X has shown a tremendous success on the
market. A wide variety of applications followed with tap water pipes and radiator connectors,
connection hoses for refrigerators and washing machines, and pipes for difficult industrial
applications. In 1988 PE-X started to be used in buried pipelines in the supply of gas and
water with diameters of up to 250 mm. During the 1990s PE-X was approved and introduced
for indoor gas installations in some countries. A number of properties such as high resistance
to stress cracking, high flexibility and low weight have contributed to the success of PE-X
pipes on the market. There are three commercial technologies to make PE-X today; by
peroxide, by irradiation and by silane crosslinking. In this paper new innovative materials and
crosslinking catalysts for silane crosslinking are discussed.
WHAT IS PE-X? SOME ASPECTS

PE-X stands for Polyethylene X-linked (crosslinked). Many other abbreviations have been
used in the past, such as XLPE or VPE (in German). The formation of PE-X is often
described as the formation of a three dimensional network where crosslinks tie the crystalline
areas together, in coexistence with a certain quantity of non crosslinked molecules. An
attempt to illustrate this is given in figure 1.

Non crosslinked Crosslinked

“Network”

Figure 1. Schematic presentation of crosslinked PE. The straight lines represent crystalline material where
molecules are well structured. In between unstructured molecules exist (amorphous areas). Crosslinking ties
crystalline areas to each other.

By indirect means we can find out other parameters characterising the network that we have
no chance of seeing at all. Using the classical theory of rubber elasticity we can estimate the
proximity of the cross links in the PE-X material. For peroxide cross inked and electron beam
crosslinked PE, typically used for pipes, we have measured crosslinking densities of 4.000-
12.000 g/mole [1]. The crosslinking density is the average length of the polymer chain
between two adjacent crosslinking points. In other words the generated data suggests that
there are on average between 300 and 800 carbon atoms between the crosslinking points. For
silane PE-X piping materials we have preliminary calculations showing similar values.

POLYMERS AND MANUFACTURING TECHNOLOGIES

Polymers used for the manufacture of high quality PE-X pipes are tailor made. It is simply not
possible to use any PE polymer for this purpose. The polymer selected must show a
reasonable crosslinking response to peroxides or an irradiation source. To make a good silane
cross linkable compound the polymer must for example be able to graft conveniently. Many
of these different properties can be derived from standard polymer characteristics like
molecular weight, molecular weight distribution and amount of unsaturations. Additives also
play a central role. In addition the pipe stiffness should be lowest possible for high flexibility
whereas high pressure performance should be maintained, in itself two contradictory
requirements.
Three major technologies currently exist for the conversion of PE to PE-X; crosslinking by
irradiation, by peroxides and by silane technology. These three groups can be further divided
into subgroups. This is shown in figure 2. It is today common to use the following
designations for the three different technologies:

PE-X-a – Crosslinking by peroxides


PE-X-b – Crosslinking by silanes
PE-X-c – Crosslinking by irradiation
Figure 2. Commercial PE-X pipe production technologies. Some examples of sub technologies are given as well.

SILANE CROSSLINKING TECHNOLOGY

The principle of silane crosslinking is utilised in several technologies; “Sioplas”, “Monosil”


and co-polymers. Common names for all of them are “Silane PE-X” or simply “PE-X-b”.
Regardless of these different names, the basic principle is said to be borne with the work
patented by Dow Corning in the late 1960s and beginning of the 1970s [2, 3, 4]. This is today
known as the Sioplas technology where PE is grafted with vinyltrimethoxysilane (VTMS) and
pelletised in a compounding machine. The grafted compound is then mixed with a catalyst
master batch at extrusion for conversion to pipes, see figure 3.

Figure 3. Silane PE-X pipe extrusion by Sioplas technology

Later on Maillefer introduced the so called Monosil process [5] where all components are
mixed in the pipe extruder itself without a prior grafting step. Co-polymers were finally
introduced on the market in the 1980´s. This paper is mainly focusing on the Sioplas
technology.

CATALYST TECHNOLOGIES FOR SILANE CROSSLINKING


– NEW EFFECTIVE SOLUTIONS

To achieve reasonable crosslinking rates it is necessary to add a catalyst master batch at


extrusion as shown in figure 3. In addition some kind of post extrusion treatment at elevated
temperature is necessary by applying steam saunas, hot water baths or simply by purging the
pipes with hot water. Catalyst systems used in the pipe industry have all been based on tin,
usually di-butyl-tin-di-laurate (DBTL). The tin catalyst and the post extrusion treatment
enables the pipe to achieve the 65% degree of crosslinking required by the specification
within a few hours for a standard plumbing pipe (say 16x2 mm). This should be compared to
several months needed to crosslink at ambient conditions. There are however some drawbacks
connected with the post treatment of the pipes, e.g. cost for the handling of an extra
production step, investment in equipment and space for hosting the equipment.
In the 1990s it was however discovered that carboxylic acids could act as catalysts in the
crosslinking of silane grafted PE [6]. An intensive development work followed and in 1999 an
optimised catalyst system (Ambicat) was launched on the market targeting the Wire&Cable
market. As this novel technology also looked attractive for the pipe market, further work has
been done in order to transfer it to the world of pipe manufacturing. The new Ambicat
version for silane PE-X pipe manufacturing was recently launched on the market. By using
this novel technology there are possibilities to avoid the previously mentioned drawbacks.
This technology allows desired crosslinking to take place within a week at ambient
conditions, i.e. at room temperature and by using the moisture of the air. Of course,
crosslinking time will be influenced somewhat by the temperature in the room as well as by
the actual moisture content in the air. As an example, crosslinking time will be shorter in the
Amazonas (40°C/100% relative humidity) compared to elsewhere. Examples of practical
crosslinking performance are shown below. For those who wish to, the new Ambicat
catalyst technology can be used with a number of different pigment master batches.

NOVEL MATERIALS WITH ENHANCED FLEXIBILITY

Not only the development of crosslinking catalysts is important, but also the base material.
Normally PE with relatively high density is used for silane crosslinkable piping materials,
often 945-950 kg/m³. The reasons behind is mainly to be in a position to meet the demanding
requirements of DIN 16 892 and EN ISO 15 875 HD-PE-X norms. However, in recent years
there has been a strong demand for more flexible solutions on the market without sacrificing
the level of pressure test performance, i.e. in many cases the HD-PE-X norm should still be
fulfilled. Recent development has shown that with modern ways of making PE, it is possible
to combine improved flexibility with fulfilment of the HD-PE-X norm [7]. Modulus of
elasticity for such a material is around 600 MPa as measured according to ISO 527. Pressure
test performance for the same grade is shown in figure 4. Requirements by EN ISO 15875
(DIN 16892) are given as reference.

Figure4. Excellent
performance of the novel highly
flexible grade in hydrostatic
pressure testing. Solid lines:
EN ISO 15875[DIN 16892])
A clear conclusion must be that this relatively flexible material meets the HD-PE-X norm
with margin. Another interesting feature of this novel material is the outstanding resistance to
thermo-oxidative degradation, or time to stage III [8]. Accelerated pressure testing of pipes
was performed at 120 °C and the longest testing time is almost 20 000 h. Using the Arrhenius
relationship between temperature and time to failure (acceleration factors), a life time of more
than 140 years [9] was estimated for a pipe used at 70 °C, which is a normal operating
temperature for plumbing applications.

Due to its high flexibility this novel silane PE-X material is particularly useful when it comes
to heating applications in general and for floor heating in particular. Other areas are drinking
water installations, indoor gas distribution or aluminium multilayer constructions. The high
flexibility also has a potential in relining situations in particular when the old pipe to be
replaced risks to give rise to notches in the new pipe. Other examples are the use of this PE-X
material as an outer or inner protection layer of large diameter pipes. These protective layers
are often thin and can therefore easily be crosslinked at ambient conditions without the need
for a separate crosslinking step.

NOVEL MATERIALS WITH HIGHER MRS RATING

In the late 1980s the so called PE100 materials were introduced on the market for gas and
water pipes having a pressure class of MRS10.0 (Minimum Required Strength of 10.0 MPa
after 50 years at 20 °C). Later on, during the 1990s, high performance crosslinked PE was
introduced on the market [10] meeting common PE-X standards. Recent development has
further enlarged the scope for PE-X within the pressure pipe area to cover also MRS10.0 and
MRS12.5. These materials are excellent for use in traditional PE-X applications such as
plumbing and heating complying with common PE-X norms or for the use in different
multilayer constructions such as aluminium multilayer pipes.

However, they are also intended for use in new areas such as large diameter pipelines for gas,
water and industrial use. Another interesting field is definitely relining of different kinds
where the variety of superior PE-X properties (like high stress cracking resistance) can be
fully appreciated. See figure 5.

Figure 5. Re-lining by burst lining


The MRS10.0 classification makes it possible to use the material in combination with PE for
the production of PE100 multilayer pipes where the PE-X layer acts as an outer and/or inner
protection layer in e.g. relining systems or industrial use. Another interesting feature of these
novel materials is the outstanding resistance to thermo-oxidative degradation as revealed by
pressure testing at 120 °C for almost 20 000 h. Using acceleration factors, a life time of more
than 140 years was estimated at 70 °C [11].

EXTRUSION

Good extrudability is obviously of great importance for all materials used for pipe
manufacturing. Parameters of special concern may be line speed, dimensional stability,
surface smoothness, surface gloss and die drool. Another important issue is sometimes the
possibility to run the materials on different extruder types. Therefore these new silane PE-X
grades have been tried on several commercial extruder lines both for solid wall extrusion and
for aluminium multilayer design. In table 1 some general data is presented that intends to give
a general impression of successful extrusion conditions for representatives of these new silane
PE-X grades using either a traditional tin catalyst master batch or a master batch based on the
novel Ambicat technology.

Extruder Melt temp. Line speed Processing Pipe surface Dimensional Die drool
manufacturer (°°C) (m/min) aid* (%) stability
Maillefer 205-235 20-40 0.75-1.5 Good Good No

Battenfeld 205-235 20-40 0.75-1.5 Good Good No

Bandera 205-235 20-40 0.75-1.5 Good Good No

Al-multilayer 205-235 20-40 0.75-1.5 Good Good No

* To be added either as separate master batch or included in the catalyst MB

Table 1.

CROSSLINKING PERFORMANCE

As mentioned earlier it is normally required to use some kind of post treatment of the pipes
after extrusion in order to achieve a reasonable rate of crosslinking and to assure the quality of
the pipes before leaving the pipe manufacturing plant. Treatment with water at elevated
temperatures, e.g. in steam saunas, hot water baths or simply purging with hot water, or any
combination thereof, is normally used today. However, by using the Ambicat crosslinking
catalyst this kind of extra treatment step is unnecessary. After extrusion of the pipes,
crosslinking takes place at a reasonable rate at ambient conditions. One example of this is
shown in figure 6 where pipes of different dimensions are crosslinked at 23 °C and 50 %
relative humidity. A standard pipe used for plumbing and heating installations of 2 mm wall
thickness is hence fully crosslinked within ca 4 days under these conditions whereas a
somewhat thicker pipe, 32x3 mm, needs approximately 10 days to reach less than 100 % hot
set. A hot set value of 100% corresponds to ca 65% degree of crosslinking as measured by
extraction method. The Hot Set method [12] is commonly used since many years in the wire
and cable industry to assess crosslinking performance. We have concluded Hot Set to be a
more suitable method to assess crosslinking when it comes to the highly effective systems
described in this paper.
Of course, the new material systems can also be crosslinked in hot water in order to speed up
the crosslinking process further if needed. It may be desirable to accelerate crosslinking this
way when thicker dimensions are handled. Figure 7 shows some results. It can be seen that
also thicker pipes, like 5 mm wall, can be crosslinked in relatively short time. It should be
noted that the crosslinking degree discussed here is the average through the whole wall.

Figure 6. Time to reach < 100% hot set (~65 % degree of crosslinking) at
23 °C and 50 % relative humidity using Ambicat and novel flexible pipe grade

Figure 7. Time to reach 65% crosslinking degree in water at 95 °C using the


novel flexible pipe grade and Ambicat or tin based catalyst.
 AND NOVEL FLEXIBLE PIPING
PRACTICAL EXAMPLES USING AMBICAT
GRADE FOR PE-X-B

The use of the new resin developed for the production of pipes made of PE-X-b with silane
crosslinking, combined with the new Ambicat catalyst has permitted to manufacture a pipe
of optimal performance from a thermal and mechanical point of view and also to speed up the
phase of crosslinking. As proved also from pipe manufacturer’s laboratories, this pipe passes
successfully the tests contained into EN ISO 15875 (DIN 16892) standard and it is very
flexible, thus by making its use easy and practical.

In particular, it is intended to develop the use of this new pipe in well-established applications
such as floor heating and in the future for the connections of the new ceiling cooling and
heating systems.

Referring to floor heating system, the flexibility of this pipe makes it ideal for installations to
be used in houses (figure 8) and into industrial installation either laid on pre-formed panels
(figure 9).

Figure 8.

Figure 9.
Or on ground treated with other insulation and the pipe fixed on suitable bars as in figure10.

Figure 10.

Its flexibility is a great help for the installer thus by making quicker and easier the
connections to the radiant circuits to the distribution cabinet (Figure 11).

Figure 11.

Its dimensional stability and its flexibility will make it essential for the connection of the
radiant ceilings, where these features shall be well accentuated for the correct functioning of
the system as shown in figure 12.

Figure 12.
REFERENCE LIST
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2. M. Narkis, A. Tzur and A. Vaxman, Polym. Eng. Sci., 25, 13 (1985)
3. B. Thomas and M. Browrey, in: Crosslinked polyethylene insulations using the Sioplas technology, Wire J.,
10, 88-92 (1977).
4. C. Maillefer, Tech. Pap. Reg. Tech. Conf., Soc. Plast. eng., (New thermoset Dev., wire cable insul. June 19-
20), 12-24 (1979).
5. L. Panzer, Union Carbide Corp., Advances in Silane Crosslinking of Polyethylene, ANTEC´88, p. 1421-4.
6. M. Palmöf and T. Hjertberg, Journal of Applied Polymer Science, Vol. 72, 521-528 (1999)
7. Product News, Borealis, No. 16 (11.2003)
8. Ifwarson M, Erisson P, Zwölf Jahre Erfahrung bei der Untersuchung von vernetztem PE. Kunststoffe 76
(1986) 3, page 245-248
9. Bodycote report/P-02/34
10. M. Palmlöf and Frank Haizmann, “PE-X for gas and water pipes”, Plastics Pipes XI, Munich, Germany 3rd-
6th September 2001, Conference proceedings.
11. Bodycote report/P-02/35
12. IEC 811-2-1 (1986)