Surface Coating for High-Performance Composites

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CCotner

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A comment Bandman444 made in a previous thread about painting on epoxy reminded me of my interest in starting a thread on this topic. The basic idea I have seen in lots, lots of places: if the underlying structure is somehow inferior or insufficient, adding some sort of surface treatment will make it better. I'm going to describe surface treatments as any sort of non-structural component which nonetheless improves performance (adding layers of fiberglass or carbon to existing airframes, for example, would not count, as it is adding structure in the form of the fiber-resin matrix. Some examples of what I have seen:
  • Painting on neat (unfilled and without fiber) laminating epoxy
  • 'High-temperature' paint
  • High-temperature (Cotronics/JB-weld/Proline) leading edges formed from neat epoxy
  • Metalized (often aluminum) tape
  • Filled laminating resin (fumed sillica, glass microballoons, milled fiber)
  • Purpose-formulated ablative coat

What have people done before, what was the rationale behind the decision, and how did it turn out? I want to hear from everyone. Troj? Tfish? Bandman444 et. al.? cjl? New Ocean? butalane? Frozenferrari? KenBiba? Everyone else I'm forgetting?

I'll start out. The only rocket I've designed or worked on whose' underlying structure was insufficient for aerothermal reasons was Bare Necessities, the N5800CS minimum diameter we are currently re-designing to take advantage of both our newly developed knowledge of high-altitude recovery and payload design and some exciting new recovery electronics (the AIM EXTRA). I calculated that, based on a worst-case (highest-performance) simulation of the first few seconds of flight, the rocket would spend approximately 14 seconds under conditions where aerothermal loads on the nosecone would be doing permanent and irreparable structural damage to the fiberglass/resin matrix. To combat this, we chose a surface coat of the same 300F laminating epoxy we used in the bulk nosecone, mixed >%50 by volume with hollow glass microballoons. My rationale for this was that the surface coat (~1mm thick, or over 4700 individual microballoons thick by quick estimate) would have a very, very low thermal conductivity-because the stuff was mostly air inside the bubbles-and that as the epoxy melted out from around an individual microballoon, it would simply strip off-exposing the next microballoon to the airstream, which would be still relatively cool, due to the low thermal conductivity of the matrix. I figured that the ~1mm thick layer would provide the required protection time, and even after it stripped off, the underlying structure would still be cool, certainly well below its softening temperature. We had considerably difficulty applying the stuff neatly, and it required extensive sanding, resulting in an unattractive and un-aerodynamic lumpy finish; overall the experience felt unprofessional. And of course, we never got the chance to test it, and that nosecone will not be flying ever, because we see no reason to risk it (we're pretty confident it would be fine; however, we have time and eventually will have the money, so why not do it over again to be better?)
 
High temp epoxy is generally misunderstood durring the cure. its important to ramp up, hold, then cool. If you do not cure the epoxy properly it will not hold up the the heat and with the cost of high grade high temp resin its worth it to cure it right esp dealing with the temps, altitudes, and speeds you are working with. I have never heard of microballoons being used for temp protection and i cant imagine it ever filling quite right. Some sort of ceramic route sounds much closer to what you need. I don't know how you would go about doing that, but i would like to see it.
 
Adding non reinforced resin, will add nothing to your performance or add to the strength of the "inferior" underlying parts.

Aluminum tape can be successfully used on flat surfaces into the sub mach transsonic range .75 to .85ish mach, This stuff will surprise you. It will not add to strength, and will more than likely conduct more heat than a standard glass resin lay up aluminum gets hot quick and easily.

High temp paint may be interesting, but i don't know if it will disapate heat as much as it will just stand up to it will peanut buttering the resin underneath.
 
I don't know if a veneer coating is up to the task. I just think it would migrate (or be blown-off) the sub-structure.

I think you need to think more in terms of the Apollo heat shield.

A snip from a NASA document (Apollo Heat-Shield Test Results):

Avcoat 5026-39/HC-G is an epoxy novolac resin with special additives in a fiberglass
honeycomb matrix. In fabrication, the empty honeycomb is bonded to the primary
structure and the resin is gunned into each cell individually. Reference 2 contains a
description of the material fabrication. The overall density of the material is 32 lb/ft3
(512 kg/m3).
The char of the material is composed mainly of silica and carbon. It is necessary
to know the amounts of each in the char because in the ablation analysis the silica is considered
to be inert, but the carbon is considered to enter into exothermic reactions with
oxygen. The char was obtained by a thermogravimetric analysis. The results are shown
in figure 9, where the percentage of weight remaining is plotted as a function of temperature
for a heat rise of the material of 39.6O R (22O K) per minute. At 2160O R (12000 K),
54 percent by weight of the virgin material has volatilized and 46 percent has remained
as char.

If it were me, I would figure out how to replicate this as best as I could. Then after the layup had been cured, CNC the nose cone to the desired profile. And we know the Apollo heat-shield material worked.

https://www.apolloartifacts.com/2008/01/apollo-9-heat-s.html

Greg
 
High temp epoxy is generally misunderstood durring the cure. its important to ramp up, hold, then cool. If you do not cure the epoxy properly it will not hold up the the heat and with the cost of high grade high temp resin its worth it to cure it right esp dealing with the temps, altitudes, and speeds you are working with. I have never heard of microballoons being used for temp protection and i cant imagine it ever filling quite right. Some sort of ceramic route sounds much closer to what you need. I don't know how you would go about doing that, but i would like to see it.

We certainly do cure correctly; on Bare Necessities' nosecone, we ramped the temperature up to the glass transition temperature (300 F) continuously for 18 hours and let it sit there for 12 hours, if I remember correctly. Something like that; we called PTM&W and they said that it was fine. We have access to a Thermotron environmental chamber which can control the temperature precisely according to a preprogrammed profile, so PTM&W said we didn't have to do the typical ramp, hold, ramp, hold that is recommended for people without the capability for sloooooow temperature ramps.

Also, from what I've seen the non-reinforced resin is usually applied to combat delamination from the leading edges of fins, not actually adding strength.
 
I don't know if a veneer coating is up to the task. I just think it would migrate (or be blown-off) the sub-structure.

I think you need to think more in terms of the Apollo heat shield.

A snip from a NASA document (Apollo Heat-Shield Test Results):



If it were me, I would figure out how to replicate this as best as I could. Then after the layup had been cured, CNC the nose cone to the desired profile. And we know the Apollo heat-shield material worked.

https://www.apolloartifacts.com/2008/01/apollo-9-heat-s.html

Greg

That is a high-temperature ablative, though. It will get hot enough for our nosecone to turn into a puddle before it starts ablating.
 
It seems to me that what is needed is a material with poor thermal conductivity that either ablates (carrying heat away) or forms a char layer (reduces thermal conductivity). Are phenolics and modified phenolics practical for our use? In other words, much the same sort of stuff we might successfully use for motor liners.

https://www.engineeringtoolbox.com/melting-temperature-metals-d_860.html
https://en.wikipedia.org/wiki/List_of_thermal_conductivities

Something I played with a few decades back was epoxy highly loaded with three micron aluminum oxide. I think there are plenty of creative things we can do.

https://www.summitracing.com/parts/RLL-248908/ - perhaps even just a coat of paint can help. That is if one can get sufficient adhesion that the paint won't chip off. That might require some form of wet sanding with a high temp primer of some sort if the substrate is aluminum.

https://www.hitempcoatings.com/pdf/1050ZN_2012.pdf

Gerald
 
I think that is what I meant. The test shows a high internal temp and much lower extirior temp. So I figured it would do the same if reversed like we would find in rocketry.
 
if the substrate is aluminum.

Aluminum would be able to handle our flight profile with a bare surface, as long as there was some other metal at the tip. Our concerns were for composite structures, which we chose for radio transparency reasons (GPS).

Also, many high temperature coatings (not all, many) have metal particles in them which also hurts radio transparency.

Nonetheless, powderskierman, that's an interesting idea, if we can get an ablative to sit on top of an insulating coating. But there is no control shown in that pdf; we don't know what a normal exhaust system's temperature differential would be.
 
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High temp epoxy is generally misunderstood durring the cure. its important to ramp up, hold, then cool. If you do not cure the epoxy properly it will not hold up the the heat and with the cost of high grade high temp resin its worth it to cure it right esp dealing with the temps, altitudes, and speeds you are working with. I have never heard of microballoons being used for temp protection and i cant imagine it ever filling quite right. Some sort of ceramic route sounds much closer to what you need. I don't know how you would go about doing that, but i would like to see it.

Can you clarify what you mean by filling right?
 
It seems to me that what is needed is a material with poor thermal conductivity that either ablates (carrying heat away) or forms a char layer (reduces thermal conductivity). Are phenolics and modified phenolics practical for our use? In other words, much the same sort of stuff we might successfully use for motor liners.

Gerald

Yeah, I wish. I haven't found a source for phenolic resins anywhere on the consumer level. I assume this is due to the relatively high toxicity of uncured phenolic resin.
 
Yeah, I wish. I haven't found a source for phenolic resins anywhere on the consumer level. I assume this is due to the relatively high toxicity of uncured phenolic resin.

Most special application ablative coatings will be out of reach of the average consumer. You could put break a few fire bricks put them in an industrial shaker and mix the powder into an epoxy paint... I have no idea if it would work but it sounds good lol
 
How hot is the nose cone expected to get and for how long? Do you have a time v temp graph?

On one of the hypersonic X-15 flights, they applied an ablative coat to the airframe, which made it a pinkish-white color. IIRC, it was an RTV like substance.

Greg
 
I don't, because there aren't any good simulators on the internet/market that can sim it except for RASAero (which itself is questionable for several unknowns, based on ongoing discussions with Chuck Rodgers), and RASAero is pretty limited on output options. If someone wrote a package for openrocket that accurately did supersonic drag, then it would be easy to define custom expressions as outputs and plot temp vs time.

What I remember off the top of my head was at 2.2 seconds or so after ignition, the stagnation temperature along the nosecone skin was above the glass point of the structure: 300F. It returned to 300F at 18.2 seconds after ignition as it coasted down through mach 2 or so. As I quickly mentally repeat those calculations I'm not convinced I did them correctly, but I don't have time tonight to fix it.
 
Worth keeping in mind that aluminum loses its temper long before it gets to its melting temperature. The temper disappears by about 450F. The strength is greatly reduced.

Gerald
 
Just because I did not remember the values, I did not mean to imply that we hadn't modeled the aerothermal conditions. The java app is sort of handy, but less handy than coding it into RASAero (or better yet, openrocket) would be.

The aeroerosion is harder to analytical model, yes. I'm investigating FEM modeling of the ablation process in a multiphysics environment. DOn't know if I have the gumption to pull that off, though.
 
Modeling the ablation itself isn't going to be as hard as finding the mechanical properties of the ablative coating at any given temperature. Without that, a model would be fairly useless.
 
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