Methanolic Corrosion of Aluminum

Inquiry

I understand that there was some issue with CableCURE^®/XL fluid when deployed in Germany in aluminum stranded cables. How do Novinium’s Ultrinium 732 or 733 fluids interact with aluminum stranded cables?

Response

It is true that about 1% of cables treated in Germany in 2002 with CableCURE/XL fluid failed because of the methanolic corrosion of aluminum. Even though the incidence of failures was quite low, the failure mode was dramatic as illustrated nearby. See the image labeled “German Cable Failure” taken from Bertini, “Failures in Silicone-treated German Cables Due to an unusual Aluminum-Methanol Reaction,” (ICC October 29, 2002). In the illustration the grey material between the strands is aluminum methoxylate, the profuse formation of which caused the insulation to bulge. The bulge is described as similar to when a snake eats a rat. An analgous phenomenon occurs in low voltage cables in the presence of water. In both cases, the bulging occurs because the aluminum hydroxide or aluminum methoxylate has a very low density, or put another way, takes up a great deal of volume. Because rejuvenation is utilized to improve the reliability of power distribution cables, even a 1% induced failure rate is unacceptable.

Novinium was founded in 2003, so we enjoyed the benefit of hindsight into the methanolic corrosion of aluminum and hence we addressed this issue in all of our Ultrinium and Perficio technologies. Novinium has not had a single incident of methanolic aluminum corrosion.

To demonstrate why Novinium technology avoids methanolic corrosion, it is useful to understand the mechanism of methanolic corrosion. One compound and one element are required for methanolic corrosion to occur … the compound is methanol; the element is aluminum.

Compound

CableCURE/XL fluid, Perficio 011 fluid, and Ultrinium 732 fluid all include methoxy silanes, which react with encountered water and produce methanol as a by-product. Ultrinium 733 fluid and CableCURE/DMDB do not produce methanol as by-products, instead these fluids produce larger, less chemically reactive higher boiling point alcohols, namely 2-ethylhexanol and n-butanol.

The reaction of methanol with native aluminum (methoxylation) proceeds at a rate proportional to the concentration of the methanol. The concentration of methanol in the strands of a treated cable is influenced by four factors:

1. The amount of water that is present in the strands and the strand-shield. Less water means less methanol; more water yields more methanol.

2. The stoichiometry of the silane water reaction. Stoichiometry is chemist-speak for the ratios at which materials react. For the CableCURE/XL fluid and Perficio 011 fluids, which utilize the same monomeric silane, the maximum possible methanol concentration is about 25% by weight. For Ultrinium 732 fluid the maximum is about 20% by weight. All other things being equal, Ultrinium would enjoy about a 20% lower methoxylation rate because of the superior stoichiometry.

3. The rate at which methanol diffuses from the strand area out of the cable. The diffusion of methanol is quite fast, so the risk of methoxylation decreases rapidly for all technologies. Higher temperature accelerates the diffusion and dissipation of methanol.

4. The use of non-methanol-based alkoxysilanes reduces methanol concentration beyond the 20% stoichiometric advantage described in factor 2 above. In a patented process (U.S. patent 7,611,748 and its foreign equivalents) Novinium adjusts the formulation with more and more non-methanol-based Ultrinium 733 fluid as the anticipated temperature of the treated cable rises.

Element

Except for copper stranded cables that are immune to methanolic corrosion, at first blush it appears obvious that elemental aluminum is available in an aluminum stranded cable, but it is not. As soon as aluminum strands are drawn and laid into a strand bundle on the factory floor, the outside layer of aluminum reacts with oxygen to form aluminum oxide (Al₂O₃). Aluminum oxide forms a dense barrier that protects the underlying native aluminum metal. This aluminum oxide layer is called a patina and it protects the underlying aluminum from further corrosion.

Patina

If you take a piece of aluminum and scrape off the patina with a knife, you will see bright and shiny native aluminum underneath. In the presence of oxygen, the patina begins to reform immediately. The shiny surface will soon return to its dull grey appearance. Of course, in a power cable there are no knives scraping off the protective patina, so how did the CableCURE/XL fluid penetrate the patina? One problem with CableCURE/XL fluid and CableCURE/DMDB is the use of a condensation catalyst called titanium (IV) isopropoxide.  Also known as tetraisopropyltitanate, we will call it TIP. Over the course of Novinium’s research we learned that TIP facilitates the degradation of the patina. Novinium does not use TIP in its Perficio or Ultrinium formulations. Novinium uses a patented catalyst (U.S. Patent 7,700,871 and its foreign equivalents) that does not suffer the same problem.

A second way that the patina can be damaged is bubble nucleation or boiling. Bubbles form in microscopic cracks in the patina and their rapid expansion and sudden disappearance mechanically perturb the patina. In the discussion above we learned that Ultrinium 732 fluids enjoy about 20% less stoichiometric methanol and hence the boiling point of the mixture is higher. Put another way, it takes a greater temperature escalation for Ultrinium to produce bubble nucleation than for CableCURE/XL and Perficio fluids. The patented silanes (U.S. Patents 7,658,808 and 8,101,034 and their foreign equivalents) included in Ultrinium fluids by Novinium and our partners enjoy improved stoichiometry, mitigating methanolic corrosion. CableCURE/XL fluid is particularly egregious in this dimension, because it includes an ingredient called trimethylmethoxysilane (TMMS) that has a boiling point even lower than methanol. To mitigate the aggressive bubble nucleation of 2002 vintage CableCURE/XL fluid UTILX Corporation reduced the concentration of TMMS in CableCURE/XL by a factor of between 3 and 6. This problem with TMMS is well documented by U.S. Patent Application 2009/0114882 and its international equivalent WO 2006/119196. Besides attacking the patina the TMMS creates a fire and explosion hazard. Novinium does not use TMMS in Ultrinium or Perficio fluids.

In addition to mitigating the causes of patina damage, Novinium utilizes a patina stabilizer from BASF^®, called Tinuvin^® 123 hindered amine light stabilizer. In experiments undertaken at Novinium, Tinuvin 123 outperformed all other patina stabilizers by at least a factor of two. Tinuvin 123 has other beneficial performance attributes to extend cable life and is included in Ultrinium and Perficio fluids and its use is protected by U.S. Patents 7,658,808 and 8,101,034 and their foreign equivalents.  In a patented process (U.S. patent 7,611,748 and its foreign equivalents) Novinium increases the supply of Tinuvin 123 by increasing Ultrinium 212 fluid as the anticipated temperature of the treated cable rises.

Summary 

Novinium substantially reduces the methanol concentration using proprietary silanes, does not use low boiling and highly flammable TMMS demonstrated to cause bubble nucleation even at moderate temperatures, eliminates a patina attacking catalyst utilized in the offending formulations, and adds a patina stabilizing compound to all but prevent methanolic corrosion of aluminum in its Ultrinium formulations. Perficio technology includes the improved catalyst and patina stabilization, and does not use low boiling TMMS. Perficio suffers from a higher methanol concentration than Ultrinium technology. Perficio technology should not be utilized in high temperature aluminum-conductor applications.

To UV or not to UV

In my December 29, 2010 post at …

Crazy-Competitor-Claims

Wonderer in the Wilderness inquired …

1. How can Novinium get the same cable life extension without a soak period?  It would seem to me that Novinium puts less fluid into the cable than one would get with a soak period.

In my first post addressing this question I provided an abbreviated answer. We learned from the abbreviated answer that that when Novinium founders conceived of the first generation of treatment fluid over two decades ago we failed to check the relative diffusion rates of the phenylmethyldimethoxysilane (PMDMS) monomer and the condensation catalyst we had chosen to provide long life.  This turned out to be a grave mistake, which we have corrected.  In a subsequent post on January 3, 2011 at …

Catalytic Considerations – Component I

… I provided a more comprehensive answer, but I promised five new posts that would explain the functional improvement of the five kinds of ingredients in Ultrinium™ 732 and Ultrinium™ 733 fluids.

In this second of five sub-posts, we will explore the role of the ultra-violet absorbers (UVAs) and hindered amine (pronounced a-mean) light stabilizers or HALS.  The primary UVA is BASF^®’s Tinuvin^® 1130.  Additionally ferrocene (pronounced fair-O-seen), which was discussed in my last post, Voltage Stabilizer, is not only a voltage stabilizer, but also absorbs ultraviolet photons in the appropriate wave length.  In the vernacular, ferrocene is a “two-fer” or a “two-for-one” ingredient, because it fulfills two independent and important life-extension functions.

As you know, frog skin is very sensitive, and so I slather on the UVA (sunscreen) every time I am out in the sun – doing so helps keep me beautiful.  Cables buried one meter underground do not need protection from the sun’s relentless ultraviolet onslaught.  They do need UV protection, however, from UV that is created when space charges recombine near the ends of water trees.  Consider for example the work of Bamji, Bulinski, Chen and Densley in the Proceeding of the 3^rd International Conference on Properties and Applications of Dielectric Materials, held in Tokyo in July 1991:

“… at points of electric stress enhancement in the polymer, the light emitted during the initiation phase of electrical treeing is … due to the recombination of electrons and holes injected into the material.  The spectra of the emitted light is in the visible and ultraviolet ranges.  The ultraviolet light can photodegrade the polymer and lead to electrical treeing.”

It is easy for us all to understand how UVA materials work.  They are opaque to UV light.  The potentially damaging UV photon strikes a resonance stabilized structure in the UVA molecule, is safely absorbed, and is converted to harmless heat.  That’s how sunscreens for our skin work too.  On my skin, if I want to stop 100% of the UV photons I need to apply unattractive zinc-oxide in a thick pasty layer – yuck!  In insulation if I want to stop 100% of the UV photons, I need to apply clay – we call those insulations EPR, EPDM, et al.  So UVA materials cannot intercept 100% of the damaging UV photons.

Unlike the common experience we all have with UVA materials, HALS are not within our normal experience.  HALS are free radical scavengers and they are beneficial, because the mechanism of photodegradation involves the creation of a free radical by errant UV photons – a photon strikes an electron and imparts so much energy to the electron that the molecule, to which it was bound, can no longer hold on to it.  A free radical (an unpaired electron in the molecule) and a free electron are created.  Electrons don’t like to be unpaired, and so, they search out other electrons and try to borrow them from their parent molecules.  As they do this, they tear apart innocent molecules and generally there is still an unpaired electron after the damage from the first encounter.  The free radical survives (or spawns a daughter) and creates cascading systemic damage.  HALS quench free radicals, and here is the cool part, they auto-regenerate to a HALS after they kill the free radical.  How cool is that?  I wish they would make HALS for amphibians, because I could take a HALS pill and snack on crickets all day without worrying about the consequences of free radicals ravaging my DNA.

It gets even better.  The word “synergy” is overused in business circles and promised synergies are often quixotic.  The poster tadpole for synergy is the interaction between UVA and HALS components.  Alone, each has a positive effect on cable life, but together they work better than the sum of their parts – one plus one equals three!  Ultrinium™ 732 and 733 fluids and Perficio™ 011 fluid utilize BASF^®’s state-of-the-art Tinuvin^® 123 HALS.  As we learned in the previous post, DMDB Doubts, Tinuvin 123 also stabilizes aluminum strand patina, which all but eliminates the potential for strand corrosion suffered by older injection technology.  Tinuvin 123 provides another formulation two-fer.

For over two decades, UVA and HALS have been included in TRXLPE (tree retardant cross-linked polyethylene) formulations.  See for example U.S. Patent 4,870,121, "Electrical Tree Suppression in High-voltage Polymeric Insulation,” September 26, 1989.  With the introduction of Ultrinium™ 732 and 733 fluids, Novinium delivers improved UV stabilization using the best available technology.  Novinium’s UV package is protected by U.S. Patent 7,658,808 and other pending patents and their foreign equivalents.  Only Novinium rehabilitation technology provides UV stabilization in the proper UV range.  To learn how first generation technology fails to address the UV photons created by space charge recombination, see Section 8 of the CIGRÉ Canada paper of October 18, 2010, “Cable Rejuvenation Mechanisms: An Update.”

To UV or not to UV, that is the question.  Answer:  Come out of the sunlight into the shade; live longer and with greater reliability,

Thermonuclear