Calcium Hardness (CH) for Vinyl Pool Liners

[chem geek]

There is this discussion (http://www.troublefreepool.com/did-you-know-that-vinyl-liners-contain-calcium-t30657.html#p252451) over at Trouble Free Pool that has uncovered the apparent fact that granulated calcium carbonate is the common filler in vinyl pool liners. I thought I'd bring that discussion over here as well.

I think that in practice it's not an issue given no problems actually seen with many pool owners having low CH water and vinyl pools, but I had always assumed there was no calcium carbonate in such vinyl liners and that apparently is not the case. The questions are whether it actually dissolves in low CH water vs. being bound more tightly in the vinyl matrix and whether even having it dissolved matters.

[CarlD]

Going into my 9th season with my liner without ever worrying about calcium in the water levels. When I test it, it's always low. You'd think after 9 years a problem with low calcium would have cropped up. It hasn't.
That's one data point.

[madwil]

CH in a chemical formula is Carbon and Hydrogen- Ca is Calcium- the guys at TPF are mixing apples and oranges!
CH is Calcium Hardness in water testing, not a chemical formula...
But I guess they figured that out themselves- lol!

[chem geek]

No one at TFP was mixing anything up. It was a guy at a pool store who got it wrong and the poster at TFP knew that, tried to explain to the pool store person what a hydrocarbon was (i.e. CH is carbon with hydrogen attached) and started the thread as an example of the mis-information at some pool stores. The thread title was facetious.

Thanks Carl. That's really what I'm looking for -- real-world examples of older liners in pools with low CH with no problems and not seeing any examples of ones with problems, at least not in any higher proportion than in water with higher CH. Also, I wanted to let people know here that indeed there may be some calcium carbonate in vinyl liners so that no one says that there isn't. We can still give appropriate advice and say that lower CH isn't a problem, but we shouldn't say that vinyl liners don't have any calcium carbonate whatsoever. It would be nice to know chemically why it may not matter, but real-world positive results will do.

[CarlD]

Hi Richard,
I don't track TFP's stuff at all so I wouldn't know. I think the other mods have a similar experience to mine, and I know Al and Lisa have vinyl liners. I'm 99% sure Jan does too, and we all never bother with calcium levels. Al's liner has got to be close to 15 years old, too.

You'll need about 15 data points before you can legitimately determine a statistical trend--too much noise below that.

Meanwhile, don't you have a scrap of liner around you can grind up and test for calcium carbonate? Give me a couple of more years and I may be able to give you mine!

Carl

[aylad]

My liner was 9 years old when I had to replace it, and the original rips that caused the need for replacement were well above the waterline, not below....

The calcium in our fill water is less than 20 ppm and I think I might have used cal-hypo for chlorination 4 times in that 9 years, in a pinch when I was out of bleach. So you can add that one to the count...

Janet

[PoolDoc]

Hi Richard, All;

Richard, if you can dig to the bottom of this, it would be very helpful to many. I did some work on it years ago, but ran into problems and gave it up. A lot of my info came from a product engineer at Canadian General (http://www.cgtower.com/). At that time (15 years ago), they were making a big part of the PVC sheeting used by US liner mfgs.

What I learned from him was the following:
+ calcium carbonate is used as filler in some, but not all (he thought) sheet.
+ low calcium was not (he thought, supported by some casual testing) going to cause premature failure.
+ like other flexible PVCs, vinyl sheet is a mixture of PVC, plasticizers, UV stabilizers, colorant, filler, and ??
+ there is no standard formulation.
+ liner color may, or may not, be in the sheet.
+ liner patterns are printed on by the liner mfg.
+ at that time (as I recall) he thought that NONE of the liner mfgs were sheet mfgs.
+ there were 2 or 3 mfgs of sheet.
+ sheet formulation was proprietary and varied from company to company, but also from time to time.
+ the same model & weight of liner might be actually made from 3 or 4 different instances of sheeting, each with different composition and properties.
+ many of the liner mfg did not understand the intricacies of PVC mfg, and thus did not understand what they were buying. There particular concerns often focused on manufacturing properties, like print-ability and suitability for their equipment.
+ printing ink varies too, and there's no guarantee that the ink for a particular model is the same over time.
+ generally, low pH tended cause plasticizer leach-out, but he didn't have data tying time and pH to damage.

Bottom line for me: there was no way to tell from one liner to another, or even from one liner today to the same liner tomorrow, and thus there was no valid way to get very specific about what would affect which liner in what way. Even with the minimal exposure to liner pools I've had, I've seen big differences in liner life expectancy in similarly managed pools.

Ben

[PoolDoc]

Whoop! Whoop! Whoop!

CGT is now making finished sheeting and has a BUNCH of tech data:
http://www.cgtpoolliners.com/cgt-technical-manual.htm

I'll archive copies, but don't have time to read it all now.

Ben

The content in this one will be particularly of interest:
http://www.cgtpoolliners.com/cgt-technical-manual-2008/cgt-technical-bulletin-4.htm

(I lied; I've ended up reading quite a bit as I archived. A lot of the data dates to 2007)

[PoolDoc]

Ok, I got side-tracked, and called CGT. I'm ADD and eternally curious; whaddya expect?

Spoke to a liner product engineer, "Immanual + foreign last name" -- it bugged him that I couldn't understand his name, I so I gave up. After we spoke for awhile, he transferred me to "Carl Flieler" (sp?) => Carl Flee-ler who is the pool liner guy, but he wasn't in.

Anyhow:

+ OK pH range is 5 - 9
+ The idea of adding calcium carbonate scared him, because he said high pH is more damaging than low pH.
+ There are definitely variations in liner material quality, and there is imported knock-off material. But he thought the patterns (see website) are likely to indicate source fairly well.

Richard, you might want to talk to 'Flee-ler'.

Ben

[giroup01]

http://piscines-apollo.com/docs/chemicals_and_vinyl.pdf

[chem geek]

Ben,

Thanks for those links. This one (http://www.cgtpoolliners.com/cgt-technical-manual-2008/pool-liner-care.htm) says under "Calcium Hardness Check", "Calcium levels should be kept at a minimum level of 200 ppm to avoid corrosive conditions. Calcium levels over 500 ppm may cause problems such as cloudy water or scaling on the liner surface." (this link (http://www.cgtpoolliners.com/cgt-technical-manual-2008/cgt-technical-bulletin-2.htm) also says CH should be a minimum of 200 ppm). Of course, the "corrosive conditions" they are talking about are the ones people refer to for metal corrosion if there isn't a thin coating of calcium carbonate and that's a debatable and controversial topic (see this link (http://www.corrosion-doctors.org/Cooling-Water-Towers/corrosivity.htm) for one such discussion) and they say nothing about low calcium doing anything specifically to the liner itself. Other CGT links refer to low pH being the real culprit along with very high chlorine level such as found by placing a Trichlor puck on vinyl (which is also low pH). They recommend using Cyanuric Acid, which as we know will reduce active chlorine level so reduce the effects of bleaching for the medium blue that is apparently the only one affected by chlorine.

The link from giroup01 (thanks for that) says the CH should be a minimum of 100 ppm. However, the lab studies looking at different water parameters found that low and high pH were the most problematic while high chlorine levels could fade vinyl and also accelerate the effects of low pH. The ideal pH was between 7.0 and 7.5. Below 7.0 there was in increase in wrinkling, loss of tensile strength, elongation and fading. Above 7.6, the vinyl loses weight and expands. As for chlorine, it should be noted that they had a starting CYA level of 100 ppm which is rather high. The FC of 20 ppm in these conditions adversely affected the vinyl (interestingly, this is only an active chlorine level of somewhere between 0.1 and 0.4 with equivalent FC with no CYA of 0.2 to 0.8 so not really that high and we've had people shock with an FC that is up to 40% of the CYA level without bleaching liners, so I don't know why they saw that unless the chlorine test didn't have CYA the way their pH test did). Unfortunately, they did not test for varying CH, but since their tests were at a CH of 100, that at least doesn't seem to be a problem level in the short-run.

Richard

[CarlD]

It's beginning to look like empirical evidence from users may be the proper foundation of a test protocol. But there has to be a quantifiable way to measure damage to the liner, compared in a double-blind setup.
In other words, you first have to model a behavior/reaction and then control conditions and have a viable measurement methodology.

Guess I've been in clinical trials programming too long!

Carl

[PoolDoc]

@ Carl, the real problem with ever testing liners is that it is apparently impossible to take that info to the consumer.

The product engineer I spoke to yesterday told me that there are substantial differences in the durability of one liner compared to another, but that he knew of no way a consumer could tell which was which. He even told me that sometimes liner makers use sheet from one mfg for the liner body, and from another mfg for the 'tile line'.

So, unless you had an exhaustive set of liners, and tested all of them, you couldn't determine which rules applied to all liners, and which were specific to a subset of them. Worse, even if you did determine that data, consumers couldn't use it, because they usually would not able able to determine which grade and source of vinyl sheet was used in THEIR liner.

=====================================

@ Chem_Geek,

you can read them for yourself (and probably have) but the water guides looked like boilerplate pulled from chem mfg releases, rather than anything from internal liner testing. One page even referenced a Biolab source.

Regarding pH, the engineer was pretty insistent that anything between 5 and 9 was fine.


Ben

[chem geek]

I agree with you about the water guides being a boilerplate so not very helpful in figuring out whether saturation with calcium carbonate is really needed.

I got some more info I posted here (http://www.troublefreepool.com/did-you-know-that-vinyl-liners-contain-calcium-t30657.html#p254039) at TFP where the most interesting information is that 1) calcium carbonate levels below 7% in vinyl do not significantly affect its physical properties and 2) that at such low levels even acidic conditions didn't result in a loss of flexibility and relatively little loss of weight.

So to me this means that low levels of calcium carbonate in vinyl pool liners probably wouldn't require saturation of calcium carbonate in the pool water. Though high levels of calcium carbonate in vinyl might require such saturation, such high levels are stiffer vinyl that is more susceptible to acidic conditions and general chemical attack. So hopefully, most vinyl pool liners don't contain such high levels of "filler" calcium carbonate. It's too bad there isn't an easy way to tell, though if one had a sample of the vinyl then I suppose one could see the weight loss when exposed to very acidic conditions since that presumably roughly measures the calcium carbonate content. Unfortunately, most people won't have a piece of spare vinyl from their pools let alone accurate scales and even then this test may not be definitive.

[CarlD]

Oh, I understand that there are many difficulties in setting up a test protocol. Even if we could give 100 people liners made by two different methods and test them over 5 years you would have trouble isolating out meaningful results due to variations in water condition, air temp, exposure to sunlight, levels of chlorine, pH, etc, that don't allow you to control for high and low calcium water. For the moment all we have is the testimonials of owners who have had vinyl pools for years with low calcium levels. This is, at best, very poor data, because we don't know what our population is, and we can guess that our sample is probably skewed. That's my side of the fence, the clinical trial issue.

Your side of the fence is establishing a mechanism where low CH can be shown to degrade various vinyls while high CH doesn't degrade the matched vinyl samples. You know, the chemistry side that I don't understand.

In the meantime, our anecdotal information tells us that CH for vinyl is...not proven to protect it.

Carl

[Spensar]

I bought my house 8 years ago with the pool. The liner was vinyl and 20 years old. The old owner hadn't done much to look after the pool and neighbours said they kept it from being green by tossing chlorine in it. What finally did the liner is was that it is a rectangular pool with square corners and the vinyl gave out at the corners. I have a very good pool tech that only does service, and doesn't sell chemicals and products, etc. and he inspected it when I bought the house. At that time he gave the corners 2-3 more years, and he was on the money.

Don't know if this adds anything to the discussion among the knowledgable here, just sharing experience with an very old liner.

[chem geek]

Thanks Spensar. Where you using bleach or chlorinating liquid the entire 8 years since you had the pool?

[Spensar]

Thanks Spensar. Where you using bleach or chlorinating liquid the entire 8 years since you had the pool?

Sorry, missed the question, so very late reply. 90% liquid chlorine, mainly calcium chloride and mainly at the beginning before finding this forum.

[AnnaK]

Late to this thread. If you're still interested in data points, here's mine:
+ 7 year old vinyl liner
+ have never added calcium
+ fill water has 52 mg CaCO3/L
+ pH 7.5
+ CYA 50 ppm
+ use 12% LC and trichlor

No damage, no wrinkles, nothing adverse to report regarding the liner. Some fading from sunlight - the area covered by the steps is darker than the rest of the pool.