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What actually happens when strings age?

Have always been surprised at how often people change their strings.
What is actually happening to change the sound of a string as it ages? If it becomes 'dull' or 'flabby' is it the winding or the core? Is it actually slowly stretching?
Some say it's just a buildup of finger dirt but I personally couldn't tell the difference after I soaked some strings in denatured alcohol for a week.
Maybe something's happening at a molecular level when stainless steel or nickel is under tension for prolonged period of time?
Or (ouch, cynical) is it like the old incandescent light bulbs - the manufacturers need repeat business?
Oh wise ones please enlighten me, and thank you for your collective wisdom :cool:)
[Pic: Ped on Basschat UK]
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Interesting. I have never seen frets on a double bass before.
I had some on my first one, made by a nylon line through the holes they were already there.
In the old days (16th/17th century) they were made from gut.

But you are right, the shown ones are from a bass guitar.

Nevertheless the OP is right with his assumptions. Bending stiffness changes due to stretching of the string, damping material (dirt) getting into the microspaces between the windings and the vibration of the string makes changes on the molecular level of the string (core mostly).
Also oxidation might have an influence in some way.
 
What happens? Eventually, a combination of dirt, oil, and general funk - combined with stretching and work hardening, will cause the strings to start going out of tune a lot, and also out of intonation. When they reach a point where they won't intonate at all? Well, they're finally, really dead - and you will have to spring for a new set. Or, sometimes one of them will break during the frequent re-tuning. That's a hint that Death for the rest of them is around the corner...;)
 
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Been covered pretty thoroughly. Work hardening/metal fatigue plus plain old stretching and probably a few other forces at work make the metal less resilient and flexible to vibrate freely as it used to and those rich overtones and strong fundamentals are gone now.

In addition to that you have funky dead skin paste, skin oils, sweat, dirt, dust, Big Mac residue, and oxidation. Living near salt water can effect it. Your skin chemistry plays a part too. Some people have very acidic skin oils, my best buddy can turn a set of guitar strings into rusty barbed wire in about a week of heavy playing.

Combine all that and probably some more factors and you get some dead strings. It varies by your skin chemistry, your playing style, climate, and string make and model and even your tolerance for and definition of “dead strings”. Some folks need fresh stainless zing, others need dead flats.
 
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In my younger years - and thankfully this is not really the case anymore - my sweat was acidic enough to eat little pits in the string surface and I know, from working in multiple music stores, that I wasn’t the only one with that problem. So they’d get rougher and lose that zing pretty fast.
 
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When particles of skin & dirt get pressed into the windings of a string, soaking in denatured alcohol isn’t going to magically float them out. Acetone is much better and will actually dissolve some dirt and debris, but it also can’t get everything out.

If you could put strings under tension while they were fully immersed in some type of solvent and then pluck the strings and make them vibrate, you could probably get the most debris out of the windings, but still probably not all.

Assuming you could get all dirt and debris out of the windings of a string, you still have other factors that cause strings to stop vibrating freely. The outer winding on a string gets “dented” where the strings contact the frets, which causes irregular outside diameter and can also loosen windings on the core.

Also, already mentioned, is work-hardening of metal. This is at a molecular level as you mentioned. Malleable metals become brittle and less malleable when continually “worked”, meaning continually bent, stretched, and compressed. If anyone reloads brass cartridge ammunition, you are very aware of this. Reloading requires resizing of cartridges made of brass. Resizing requires the brass to be compressed and expanded to a specific size. After this is done a few times, the brass begins to harden, and then begins to split or crack due to becoming hard & brittle.

Although nickel & steel aren’t as soft as brass, it will bend, compress and expand. After doing this for a period of time, and also vibrating (micro-bending at witness points) many thousands or millions of times, the metal will change in hardness and flexibility to some degree.

There might be multiple other things that affect string life, but I believe #1 is dirt, debris, skin oil, and corrosion from those things that does the most to deteriorate string performance. A good hypothesis for this is to consider how long piano strings last and sound much the same for years or decades. No human hands are pushing those strings against frets, and sliding up and down the length of those strings, so dirt and debris are not pushed into the windings like on bass, guitar, mandolin, banjo, ukulele, fiddle, upright bass, etc. strings.
 
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In strings with hex cores, the the corners of the hexes can get worn down over time, softening/rounding them from where the wrap touches them. In roundwound strings, the fine point of contact between the round wraps can similarly get worn and flattened slightly over time, so the contact is softened. So when you try boiling strings to rejuvinate them, you will get an noticeable effect from eliminating the residue that builds up in those spaces over time, but it still won't be as bright as brand new, and they will get dull again faster than when brand new because there is a bit more space for residue to more easily build up again.
 
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I used to boil my strings, which made them temporarily brighter. The only change I can think boiling made is funk removal, but simple corrosion must have had some part in it. In general I find stainless string retain "zing" longest, which would point to corrosion as a factor. I dont really dig flats tone, but they are much easier on the hands and frets. I use nickel rounds these days, they seem to.retain a decent balance of brightness longevity and dont chew up my fingers.
 
One thing I've noticed, that I haven't seen anyone else comment on yet, is this. As time goes by, you can see wear marks on each fret, where the fret surface has been worn down a little, and so you have four spots on each fret (on a 4-string, obviously) that look a little wider than the rest of the fret.

Well, that same flattening phenomenon happens on the underside of each string too. I have often used neon coated strings, and it's really easy to tell when they're getting old and worn. The roundwound just isn't as round any more where it meets the surface of the fret. (The same thing happens with flatwounds, too, it just isn't as noticeable.) The flatter the underside of the string, the flatter the tone.