Showing posts with label plastic. Show all posts
Showing posts with label plastic. Show all posts

Wednesday, 23 May 2018

3D Eksperten Silky Gold and Copper PLA review

I have been looking for a gold-like filament for a while, and it proves difficult to find one that has a convincing metallic appearance. Many filaments with ‘gold’ in their name are merely a yellow or orange colour with perhaps a hint of metallic additives. For instance I bought a spool of Polaroid ‘gold’ PLA and even though it is overall a good material, it proved to be merely a deep yellow with only under ideal lighting conditions a very slight metallic sheen.

A while ago I saw some makes on Thingiverse that looked quite promising, and the author was friendly enough to tell me that the filament was ‘Silky Gold’ from a Danish manufacturer called 3D Eksperten (3DE). At that time 3DE didn't ship to my home country and only offered expensive express shipping. I checked out the store again after a few months and they did ship to my country with an option of more reasonably-priced shipping, hence I ordered both a spool of the Silky Gold as well as Silky Copper. I added the latter not only to reduce the relative shipping cost, but also because it looks stunning on photos. The total cost was about €60, which means €30 per 1 kg spool which is reasonable for a specialty filament. In hindsight I should also have added a spool of Silver to have a full set of shiny metals, so I know what to buy the next time.



Despite the cheaper shipping it still arrived within a mere 3 days with tracking information. The filament comes in stylish boxes and is packaged in resealable plastic bags with of course a packet of silica gel contained within. This is nice but I have learnt that all plain plastic bags are only weak barriers against moisture: they will only slow down the rate at which moisture can reach the spool. For this reason one should refresh the desiccant in such bags at regular intervals, and for longer-term storage it is recommended to use mylar bags instead. Those have a metallic layer that is much better at stopping moisture (this is why all foodstuffs sensitive to humidity are packaged in metallic bags). The desiccant inside these particular bags proved to have absorbed near their saturation level of moisture, so I dried the filament in an oven to be absolutely certain it was in optimal condition. A weight comparison however showed that it hadn't taken up any noticeable amount of moisture.

The spools themselves sure do look promising out of the box, especially the copper one which looks like a big transformer coil. I have never seen such a convincing plastic simulation of a metal. The gold is very nice as well, still obvious it is merely plastic but it comes closer than any other attempt I have seen so far. It wouldn't be the first time that printed objects lose the appearance of the raw spooled material however, so the proof is in the pudding and it's time to load up this stuff and get printing.

The tolerances on the filament are within the typical ±0.05 mm range. On the gold I measured an average diameter of 1.77 mm, on the copper 1.72 mm. These diameters remained consistent over the length of material I have used so far. The filament also appears well wrapped without risk of tangling, something that cannot always be said from the cheaper brands. I used my typical PLA settings of 200°C extrusion and 60°C bed temperature, on a glass bed with 3DLac and moderate cooling fan speed. Adhesion is excellent even with only a thin layer of hairspray. There is no obvious odour during prints, not even the typical popcorn-like smell of regular PLA.



I started out with my traditional test print, a variation on the classic 20 mm calibration cube printed at 0.2 mm layers. This already looked very promising: the surfaces are shiny enough to reflect light like actual metal albeit with a matte finish (a true mirror it ain't). I then printed the 3DHubs Marvin (or rather my ‘improved crotch’ remix, which is a good test for overhangs and rounded surfaces. These looked even better, especially the copper one which from a distance could easily fool someone into believing it is made from actual metal.

The Marvin prints do show it is even more essential to avoid visible seams with these filaments than with most other materials. The glossy effect is visibly disturbed at the places where an outer contour starts. To understand why, we need to make at least a good guess at how the metallic effect is achieved.

Left: piece of free-air extrusion, right: normal printed extrusion
Close-up view
A close-up view reveals the usual trick of mixing in little metallic specks is not being used. Instead, there is a shiny effect that varies with extrusion direction. How does it work? There are two important observations: one, both the spools and the printed results reflect light only at angles perpendicular to the direction of extrusion. Second, the filament tends to contract very quickly in the direction of extrusion when extruding in free air, and the end result loses its shiny appearance altogether and becomes a plain dull yellow or orange strand. I can only explain this by assuming that the plastic contains a kind of elastic fibres that become glossy when stretched (like silk indeed). During normal extrusion the material is not allowed to contract, which ensures that the fibres remain stretched. For the same reason you should not print this filament too slowly: if the extruder keeps heating the same part for too long, the shiny material gets too much time to lose its ordering and gloss.

This also explains why seams are especially visible: the extrusion changes direction abruptly at the start of the contour and it takes about a millimetre until the fibres are fully aligned to the new direction.
Vase mode print of thing:415360 by Alphie

There is unfortunately no magic solution to hide seams. If you're lucky, the object has enough concave corners to allow your slicing program to hide the seams inside. If not, a typical strategy is to randomise the starting point of the contours but this will leave the surface littered with quite visible specks due to the effects described above. The only way to eliminate seams is to print in ‘spiral vase’ mode when possible. I have done a few vase prints and they look impressive.


Objects with many different surface orientations are the most rewarding hence I made a vase model with faceted hexagonal outer surface specifically to showcase this filament. Also when printing coin- or medal-like models the best results are obtained when keeping the special properties of the filament in mind. Top surfaces of coins should be printed as one continuous spiral in order to get a finish that has no seams and reflects light in interesting ways.

Left coin was printed with spiral top infill, right with plain rectilinear. Model by FLOWALISTIK. (Too bad these aren't worth actual Bitcoins…)
The material proves quite tough: extruded material doesn't break easily and is not easy to cut up. If my fibres theory is correct, perhaps they also contribute to strength. While I consistently have stringing problems with almost all other PLA filaments in my Micro Swiss all-metal hot-ends, these silky filaments are much less prone to stringing, perhaps again thanks to their tendency to quickly contract in free air.

There is one problem with ordering this filament and it is that the 3DE store is mostly in Danish only. The language is similar enough to my Dutch mother-tongue that I managed to get through the ordering process with the occasional help of Google Translate, but it may prove challenging for people from other countries. Also, no shipping outside the immediate surroundings of Europe. On Amazon one can find similar filaments which might come from the same source (judging from the similar hexagonal pattern on the spools), so it is worth trying if you are not able to order from the 3DE store.

To conclude, this is a great filament for decorative pieces and medaillons or coins. The copper is obviously my favourite because it comes very close to looking like the real thing. The gold may not be able to fool anyone but still it looks better than other attempts at a ‘gold’ filament I have seen.

Friday, 11 March 2016

Undoing yellowing on ABS plastic like LEGO® bricks and old computer cases

Every owner of vintage computer hardware or older LEGO® sets will know the problem: the plastic that used to have a bright white or neutral grey colour, tends to turn yellowish or even brown over time. I used to believe this was an irreversible ageing process, until I did some research. My first find was a YouTube video presenting a rudimentary way of bringing back the bright white colour of LEGO® bricks. Further research led me to the “Retr0bright project” which presented a more advanced technique than the video.
Bromine.
Original photo by Jurii (license)

The culprit proves to be the flame retardant inside the ABS plastic. It is based on Bromine, which is not a big surprise because it has the same typical brown colour as gradually appears on the affected plastic parts. When exposed to UV radiation (which is present in sunlight), the bromine compound reacts with oxygen, causing the colour change. Ironically, the method to reverse this discolouration relies on the same UV radiation. The trick is to add hydrogen peroxide (H2O2) to the mix, which encourages the bromine compound to release the oxygen atom and put hydrogen in place, which undoes the colour change.

That is the basic idea behind the process. A refinement can be made with a chemical called TAED which can act as a catalyst to greatly speed up the reaction. This chemical happens to be an ingredient of typical “Oxy” laundry booster, so it is readily available.



I did some experiments of my own on some old LEGO® bricks of which I assumed they were doomed to be eternally bereft of their original bright white colour. As you can see in the above photo, the results are quite spectacular. Those are the same bricks (if you look carefully, the legs still have the speck of dirt on their left side). The above experiment was done with H2O2 only, and it took several days to obtain those results. The next experiment was done with Oxy added, which provided results much quicker:



The Retr0bright project used to have a wiki explaining how to make and use an optimal mixture for restoring old ABS plastic. Unfortunately this wiki is now down, and accessing it through the Internet Archive is slow and often incomplete. Therefore I will try to summarise the essential information here for easier reference, backed up by my own experimental results.


Caveats and general remarks

You will be working with hydrogen peroxide. Any solution between 3% and 30% strength can be used. The 3% variety is easily found in the pharmacy section of supermarkets etc, and won't do any harm if you only leave it in contact with your skin for no longer than a few dozen seconds. Up to 10% can be obtained from hairdressers, it is used for bleaching hair. This is more dangerous and skin contact should be avoided, also ensure it does not get into your eyes: wear goggles. Stronger solutions are more dangerous: 30% can produce instant painful burns, so never handle it without proper precautions. Needless to say: if you are a kid, you should not attempt any of this without adult supervision.

As with many chemical reactions, this one is dependant on temperature too. From my experiments, this proves to be an extremely important factor. It seems the reaction only really provides any results at all from 15°C (60°F) on, and only really starts to catch on at 20°C (68°F). Warmer means faster, but I do not recommend going above 30°C (86°F) if you want to leave the parts unattended for a longer time period. Certainly avoid going above 40°C (104°F) because parts could start to deform.

Ensure the parts are submerged at all times. Any part that is partially submerged risks developing a white sheen at the liquid-air boundary. If this does happen, it might be possible to remove the sheen by ‘burnishing’ it, i.e. rub another smooth and hard object against it. For LEGO, you could try a slightly harder plastic object like the brick remover.

More is not always better: do not be tempted to add more Oxy, stronger peroxide, heat, or stronger UV light. At some point you will be damaging the plastic beyond repair if you do.

Basic method

This method is easy and cheap, but not always practical.

  1. Find a transparent recipient large enough to hold the plastic parts you want to restore. Cover the bottom outside with tin foil, preferably with the matte side up (this will reflect light more evenly). You can also apply tin foil to the side of the recipient that points away from the UV source. If you really want to provide the most uniform lighting, put the recipient on a slowly rotating turntable.
  2. Pour the hydrogen peroxide solution into the recipient, enough for the parts to be submerged.
  3. Submerge the parts and ensure they cannot float up again, e.g. by placing a glass plate or something else transparent over it. Do not stuff too many parts together: ensure the light can reach every part.
  4. Place it in direct sunlight, or under a UV lamp that outputs a decent amount of light. For a 15 W lamp, do not put it closer than 25 cm (10 inches).
  5. Wait, stir up the recipient occasionally to let bubbles escape and to turn around parts, and take out and rinse the parts when they appear to have bleached sufficiently.
Bubbles
This method works OK, but may be slow, although it can go surprisingly fast when the liquid is warmed up to about 30°C. On a hot summer's day, parts can go from brown to bright white in a few hours. The advantage is that the peroxide solution will generally last long and can be reused. As long as you see bubbles forming on the plastic parts, the solution is still active. If no bubbles form within 5 minutes even when the solution is warmed up to 30°C, it has decomposed into plain water and must be replaced.


Faster method

  1. Do the same as above, but add a small amount of “Oxy” laundry booster to the mix. You should not add more than about 1/4 teaspoon per half litre of solution. Ensure it is well-mixed, you could dissolve the Oxy in a bit of warm water before adding it.
  2. Ensure the solution stays at about 25°C, or 30°C if you want it to go really fast.
  3. Monitor the solution carefully at regular intervals. As soon as it stops bubbling, remove the UV light source and take the parts out. If they are not yet sufficiently bleached, make a new solution.
This method can provide spectacular results within hours, even at moderate temperatures. The problem is that the solution will break down much faster, and as soon as the peroxide is gone, the UV light will again start the yellowing process. It is therefore essential to stop when the peroxide is exhausted.

Only add the Oxy when you're going to start using the solution. It cannot be stored for a long time with the Oxy added, unless perhaps you cool it down to near-freezing temperature, but I do not guarantee this.

The disadvantage is that the Oxy generally also contains detergents which will cause foam, especially with the peroxide bubbling. This will stop after a while though. The detergents may also leave a dull residue which needs to be washed off the parts. Also, see my comments about coloured parts below.

Efficient method for large parts

The above methods are unpractical for large parts like computer cases, keyboards, or LEGO® baseplates. For those, it is better to create a gel as proposed by the Retr0bright project, which can be applied to the surface with a brush. Simply place the parts with gel applied to one side in the UV light (or sunlight) and check on them regularly. Then repeat for the other side. On the Retr0bright website you can see a spectacular example of what this method did for a horribly discoloured Commodore 64, with repeated applications within a timespan of only eight hours.

I have not tried this myself yet, but a good recipe for the gel seems to be the original Retr0bright one:
  • 500ml of 10% to 15% hydrogen peroxide solution (dilute it down with distilled water if you have a stronger solution).
  • 2 heaped tablespoonfuls of Xanthan gum
  • 1 level teaspoon of Glycerine
  • 1/4 teaspoon of Oxy. Again, do not add the Oxy until you're about to apply the gel.
The same remark about temperature holds: try to keep the parts between 25 to 30°C. Ensure the gel does not dry out, replace it if it starts to dry.

Although in theory it could be omitted, the Oxy is very helpful for this method because the gel dries up within hours, therefore we can really use the extra speed from the TAED catalyst to save us from having to reapply new gel too many times.

If you do want to omit the Oxy, you will need to ensure the parts are kept at a temperature between 30 and 40°C while being exposed to the UV light, otherwise the gel will work unpractically slowly. You may be lucky that the sunlight provides exactly the right amount of heat, but for an indoor setup with UV lamp, you would need to find a way to warm up the parts to the right temperature without causing the gel to dry up quickly (a heater with a fan is obviously not a good idea).

What about coloured parts?

For LEGO®, the parts that suffer the most from yellowing tend to be the white, blue, and grey ones (obviously, on colours like yellow or red, a lot of additional yellow needs to be added for it to become visible). For white, there is not really a problem: you cannot overdo the bleaching. For colours however, the story is different, and from my experiments I can only conclude that results are unpredictable.

The hook and bottom blue plate were treated, and ended up too pale.

I tried the second method (with Oxy) on both a blue brick and grey hook that had badly discoloured. At first it got better, but in the end both parts were bleached beyond their original colour. However, I do have obtained quite good results by only using peroxide, with other bricks that were less yellowed to start with. I suspect two things: first, the pigments themselves were already damaged by the exposure to sunlight, making it impossible to restore the colour of really badly yellowed parts (unless someone would find another clever chemical process to revert that reaction). The yellow or brownish tint can be removed, but the original colour cannot be fully restored. Second, chemicals in the Oxy might further damage the pigments. I would avoid using Oxy with coloured parts. My intuition tells me that the risk of damaging the colours will be lower, the less chemicals you add to the mix, so the peroxide-only method seems safer.

If you have a really badly yellowed blue or grey part, I recommend using peroxide only without Oxy, and regularly checking on its status. Avoid strong UV exposure because it could further damage the pigments. Take the part out of the liquid as soon as it looks good enough. Maybe a slightly yellowed darker colour is preferable over a yellow-free bleak colour. You will have to accept that it may not be possible to get back the original appearance. Anyone who has more experience with restoring coloured parts, be sure to leave a comment.

As for imprints and stickers on the plastic, these will generally not be harmed by the peroxide, although I cannot give any guarantees. If you want to err on the safe side, your best bet is to use the gel method and avoid applying gel over printed logos or any other non-ABS parts.

Do ABS parts made today still suffer from yellowing?

Wikipedia states that the use of bromine-based flame retardants is declining in the Western world. I have no concrete information about this, so I did a small experiment on a recently bought LEGO® part from Pick-a-Brick. I placed it under the same UV lamp used for the above experiments, for several days. The result was no visible effect whatsoever, so I am inclined to say that recent LEGO® parts are less susceptible to yellowing than the ones from the nineties and earlier. Nevertheless, if you plan to exhibit your favourite LEGO® models in a sunlit room, it may be wise to provide some kind of UV shielding.