I work for PPG Industries
at their Coatings Innovation Center just outside of Pittsburgh.
Today I'm going to be talking about some of our experiences
with using DOE for novel coatings development,
particularly focusing on the importance of using auxiliary responses.
The agenda, I'll talk a little bit about research methodology,
and in case you're wondering what I mean by auxiliary responses,
I'll define that in this section.
Then we'll go on to two examples.
The first one, a new resin development for architectural coatings,
and the second one, a protective coating,
then we'll finish off with a few general observations.
There are various frameworks that can be used to describe
the new product development process.
One that I particularly like is shown here, DMADV.
Here we have five stages.
The first stage is to define the goals of the project.
What are we trying to achieve?
Then we get into measurement.
What are the critical characteristics we need to measure,
and do we have suitable processes in place to measure them?
Then we think about analyze .
What factors can we change to make improvements?
Then onto the design stage,
where we deliberately manipulate those factors
and the levels of those factors
to try and affect an improvement and lead to optimum performance.
Then once we have an advanced prototype, we get onto verification,
thinking about will our solution work in the real world?
What are the important things we need to think about
when we apply this framework?
Well, in terms of the defined stage, the goal needs to be clear
so that the whole organization has the same understanding of the goals,
and it needs to be impactful.
If we're successful and we deliver a solution,
will it fill a real unmet need in the marketplace
and be a successful product?
If we skip now to the end,
any solution we apply needs to be cost- effective.
It needs to be robust.
Then the middle of this process,
we want to get through this process as quickly and as efficiently as we can.
We want to deliver the product to the marketplace as soon as we can,
and we want to expend the minimum amount of cash
and the minimum amount of resource to do that.
Clearly, DOEs and a lot of the tools that are available in JMP
are well set up to make us succeed in this area.
One of the tools that I like to use
particularly early on in a project is a process map.
This is a very particular type of process map.
It's really mapping
the process of carrying out the research and development.
I'm showing here a simplified example of a process map
to develop an automotive base coat.
We have all the steps that are involved in our experiment.
We make a resin,
we use that resin to make a base coat paint,
we spray apply that base coat onto a substrate,
we apply a top coat onto that base coat,
then we cure those coatings together,
and then we measure the properties that we get from all of that.
All of these steps,
we list all of the factors that might play a role in these separate steps.
This is useful for a number of reasons.
First of all,
it gives everybody in the team a unified understanding
of what the process is we're dealing with and how are we going to affect it.
It also allows us to capture all of the variables we can think of
that might play a role in the various steps
so we don't overlook anything.
Then it's a good starting point
for thinking about which of these are we going to try and manipulate,
which of these are we going to focus on to try and deliver a successful project?
These factors are further subdivided and categorized.
First, we have our Xs.
These are the variables that we can manipulate
to try and affect an improvement in our product or our process.
Then we have our big Ys.
These probably appear in the specification of the product.
These are what we're really trying to achieve.
This is what the customer really cares about,
what the customer will pay for.
Next, we have our Ns, noise variables.
These could be variables that we may be not controlling,
we're not deliberately manipulating,
but things that could introduce noise into the process,
either during the experiments, during the new product development,
or in the end application,
in the manufacture of the product or the end use of the product.
Then finally, the subject of today's talk,
we have our auxiliary responses, which we label as little Ys.
These might not appear in the specification,
the customer might not even be aware of these,
but they're measurements we can take at various stages of the process
that might tell us something about what's going on.
I said in the previous slide that one of our goals
is to get through this whole process quickly,
as in efficiently as we possibly can.
One question that raises is, why don't we just measure our big Ys?
We have the ability to carry out DOE's.
We could optimize for our big Ys, we could build predictive models.
Isn't that all we need to do?
Why should we spend time?
Why should we spend money measuring some of these little Ys
when they're not the real goal of the outcome?
Well, I hope in the next couple of examples that I can show you,
some cases where carefully selecting these little Ys
and doing some good analysis
can be really critical to the success of a project.
Our first example here,
the development of a new resin for architectural coatings.
The goal was to come up with a single resin that could meet
all of the performance requirements
across several product lines in several countries.
Our starting point was,
we had no single resin that could meet all those requirements.
We were using different resins in different products,
different resins in different countries, and we needed to come up with a solution
that allowed us to reduce the complexity there.
Our early prototype struggled in a number of areas,
but one particular area was tint strength.
The way these white base paints would be used
is if I go into a store and request
a paint of a particular color to paint the walls of my house,
the store will take that white base paint and add specified amounts
of concentrated color toners to that paint to create a specific color.
It's really critical to be able to hit a target tint strength,
which is the measurement of how quickly that color will change
as we add a certain amount of a particular toner.
We need to be able to control that and hit it reproducibly
to achieve the wide spectrum of colors we need to achieve.
We also had a few issues in terms of poor heat age stability
and poor resin reproducibility.
Our approach was to carry out some sequential DOE's
to learn how to control tint strengths and some of the other factors.
I'm showing the progress on this plot at the bottom left-hand side of this screen.
Before we started the DOE's, just some of the exploratory experiments;
the orange bar represents the range of tint strengths we were able to achieve.
We can see that is far below
the target range of tint strengths shown by this green bar on the plot.
As we carried out the DOE's, we learned how to control tint strength.
We were able to increase it until towards the end of the project
when we were doing our optimization DOE's,
we were nicely centered around this target tint strength.
We were able to build predictive models and use those
in conjunction with predictive models for some of the other key properties
to identify white space where we met all of the target properties at the same time.
But rather than talk about the whole project,
I want to now focus on one particular DOE that we carried out.
The goal of this DOE was to confirm and quantify
something we'd observed previously,
that the particle size of the resin we were making
was a big factor in controlling tint strength.
These resins are, in effect,
dispersions of little particles of resin in water,
and it was the size of those particles that seemed to be important.
We were also using
what we call a co-surfactant to help disperse those particles,
and we had a few choices
about where in the process we could add that co-surfactant.
We wanted to look at a couple of candidates
for the addition point of that co-surfactant
to see if it affected the key properties.
Then finally, up until this point, all the resins we've made,
we've made at the Coatings Innovation Center.
We now wanted to check,
could we make these resins reproducibly across three different locations?
The DOE we carried out is shown on the right-hand side here.
We have three levels for our target particle size.
We have two levels for the addition point of the co-surfactant.
That gives us a full factorial DOE with six runs.
Then we replicated that DOE across three different laboratories.
I'll go straight into JMP
and I'll show you what the data table looks like.
You can see here we have the original data table, the DOE,
but now we have
a whole collection of data that we gathered during the DOE.
The first thing we'll do is,
we'll look at what we learned about tint strength.
I've already built here a reduced model for tint strength.
If we have a look at the effect summary to start with,
we can see that the location of addition of the co-surfactant
wasn't a factor in determining tint strength.
That dropped out of the model.
But we do see that the target particle size
and the reactor location were factors, as well as the interaction
between target particle size and reactor location.
If we look up at our actual by predicted plot,
we can see it looks like a pretty nice model.
We've got a nice R-square,
and everything looks to be in pretty good shape.
Then probably the best way
of understanding what's happening and what this model is telling us
is to look at the prediction profiler here at the bottom.
We see our anticipated effect of target particle size on tint strength.
As we increase target particle size, we get higher tint strength.
Then if we look across at reactor location,
what we see is that Lab A and Lab C are giving broadly similar results.
But if we look at Lab B, first of all,
we see that the tint strength that we get from Lab B
is significantly higher than we were getting from Lab A or Lab C.
We also see that the dependence on particle size
is much less from Lab B than we saw from the other two labs.
This was a problem for us.
Whenever we see that different labs are producing different results
with the same resin and the same process,
it can be a really long task to work out what's going on here.
There's so many potential candidates
for the cause of this poor reproducibility.
At this stage, we were very concerned
that it was going to take us a long time to resolve this,
that it was going to derail the project,
and we're going to miss our target launch dates.
Before we went into any specific activity to try and address this problem,
the obvious first step was to look
at the data that we'd already gathered in this data table
and see if there were any clues that could maybe give us a hint
as to why Lab B was giving different properties.
Whenever I see a wide data table like we've got here,
one of the first tools that I always go to is the column switcher.
The way in this case that I will implement this
is the first step is to build a variability chart
that best shows the problem that we're having.
I've pre-built a variability chart here
where I've got target particle size and reactor location as my X-axis
and I've got the initial tint strength as my Y-axis.
The first task is to get this
into a format that the best represents the problem we're dealing with.
The first thing I'll do
is swap over my target particle size and react or location.
I'll also add and connect the cell means to add some lines here.
Now I'm pretty happy with this.
I think this nicely reflects the problem that we're dealing with.
We can see Lab A and Lab C very similar results,
but Lab B, higher tint strength
and less dependence on tint strength and particle size.
Now I can use my column switcher,
and what this will allow me to do is keep this plot in exactly this format,
but quickly switch out this Y-axis, the initial tint strength,
for any other variable that I've got in my data table.
I'll go into the redo platform and select the column switcher.
Now I can select any of the other factors in my data table.
I'm just going to select everything that I've got in my data table.
Then when I hit OK,
I now have this column switcher to the left of my plot.
I can click on any of these factors
and it will change this axis but keep the plot in exactly the same format.
If I select particle size,
I can see now I'm plotting my actual measured particle size
against target particle size and reactor location,
exactly the same format.
It looks like in this case,
all three labs are giving pretty similar results.
I'm not seeing anything that gives me a clue as to what's going on,
but I can quickly just scroll through this whole data set.
I'm seeing mostly noise right now.
I'm not seeing any patterns that seem to be particularly helpful,
but I'll keep going.
When I get to this plot here, so now I'm plotting conductivity,
I see interestingly that Lab B is making resins
with much higher conductivity than Lab A and Lab C.
That's one useful observation.
I'll keep going.
This next one,
this is actually another measurement of conductivity
after the resin has been in a hot room for a week,
showing the same thing,
still confirming that Lab B is giving higher conductivity.
I'll keep going.
Mostly noise, maybe a little bit of an indication
that the molecular weight from Lab B is slightly lower.
I'll keep going.
Again, still not seeing anything that interesting, mostly noise.
But then I get to this plot here, and again,
now we're plotting the pH of the resins one hour into the process,
so early into the process, the acidity or pH of the resin.
Lab B, again, is different from Lab A and Lab C.
It's giving me much higher pH.
Keep going just to check if there's anything else.
This was the initial plot we started with of initial tint strength,
and then the last one is the paint viscosity,
where everything looks pretty similar.
Really quickly using column switcher,
I found out that not only is Lab B making resins with higher tint strength,
it's making resins with higher conductivity
and higher acidity, higher pH.
What could that be telling us?
What might be causing higher pH and higher conductivity?
Well, these resins, I said,
were a dispersion of a polymer particle in water.
Anything that's changing the conductivity, the pH is going to be in the water phase.
It's not going to be in the resin phase.
What we did was we precipitated by centrifuge,
we precipitated out the resin and just analyzed the water phase.
We carried out a lot of analysis, but one of the things we worked on,
I'm showing on this plot on the right-hand side of PPMs,
of parts per million of phosphorus and sulfur
in that water phase.
If I look at the orange bars to start with, the sulfur,
I can see all of the resin s from all three labs are very similar,
but the blue bars, the level of phosphorus,
Lab B is making resins with about four times as much phosphorus
as they were making from Lab A and Lab C.
When we looked at the recipe for making these resins,
there's only one raw material that brings in phosphorus.
On a bit of further investigation,
what we found out was the supplier that was delivering this material to Lab B
was mistakenly supplying something
that was four times as concentrated as it should have been,
and four times as concentrated as they were providing to Lab A and Lab C.
The auxiliary data that we looked at in this DOE using the column switcher,
we were able to really quickly pinpoint the cause of that problem.
We didn't have to expend time to get there.
The project stayed on track, and there was even a bonus.
We learned that increasing the level of this material with the phosphorus
was another tool we had to increase the tint strength.
We would have probably never been aware of that
if we hadn't carried out this analysis and had this happ y accident.
That's the first example.
We go on to the second example now.
In this case, we're dealing with a protective coating,
a coating that's designed to go over metal substrates like iron and steel
and protect from corrosion .
We have five experimental resins that we want to look at,
a resin that's designed to give good corrosion,
and then four resins
that are designed to improve the flexibility of the coating.
The first three of these resins
are added in the first stage of the coating preparation,
and then the last two get added in a separate later step.
We have two questions here we're trying to answer.
How do the resins affect corrosion and affect flexibility,
and what is the best combination of the levels of these resins
to give us the best combination of corrosion and flexibility?
Again, we use DOE, we were able to build predictive models,
and here we were using the mixture profiler
to identify some white space that we can work in.
This DOE is a little bit more complicated than the first one,
so I'm trying to represent pictorially what we were dealing with here.
If we look at our first stage of our coating manufacture,
in addition to our three experimental resins,
we have a main resin at a fixed level.
In effect, our three experimental resins are three mixture variables here
because they form the rest of this 100 %.
They add up to a constant sum of 57.77 %.
Three mixture variables dealing with there.
Then in stage two,
we can deal with our other two resins as independent variables
because they're not part of that mixture.
We have three mixture variables, two independent variables.
We also have some levels
that the formulators were able to decide they wanted to work in
based on prior experience for all of these resins.
Then we have some constraints on the combinations we're dealing with.
For example, at the start here,
we want the sum of Flex2 and Flex3 to be more than 10% but less than 30%.
There are some other constraints as well.
A fairly complicated DOE, but using custom design,
it's relatively straightforward to build this DOE.
Definitely some tips and tricks in terms of how to build the DOE,
what model to use, and how to analyze that data.
I don't have time to go through that today,
but I'd be perfectly happy
to talk about that offline if anybody's interested.
But let's go straight into JMP and we'll look at this example.
Here we have the DOE that we carried out.
It was a 16-run DOE.
If we go right across to the left-hand side,
we have our three mixed variables and our two process variables.
We've measured our flexibility and corrosion
and then we have a lot of other auxiliary responses we've measured.
I was able to build good predictive models for flexibility and corrosion.
What I'm going to do is just show you those models in the profiler
just to help us understand what we're learning and what's going on.
I'll add those two predictive models that I built to my profiler,
and then I get my profiler here.
I can see, first of all,
I'm plotting flexibility and corrosion here.
Lower numbers are better for both of these responses.
Lower numbers for flexibility,
lower numbers for corrosion are what we're targeting.
I can see as I add my corrosion resin, if I increase the level,
I get better corrosion performance,
but unfortunately, I get worse flexibility.
The opposite is true for most of these flexibleised resins.
As I add more of these,
I'm getting better flexibility, but worse corrosion.
This is something that's very common
in coatings development and lots of other areas.
Seems like there's always a pair of properties
where if we improve one of them, we always make the other one worse.
But if I come across to my Flexabiliser 4 resin,
something really interesting here,
as I add more of this resin, I get better flexibility,
but I don't suffer at all in terms of corrosion.
This is going to be a really useful tool
for us to optimize the combination of flexibility and corrosion.
But I'd like to understand a bit more about the science behind this.
What's happening?
What's unusual about Flex4
that allows us to improve our flexibility without degrading corrosion?
Again, I want to use all of this auxiliary data
that I've gathered in my data table to help me understand that.
What I did is, I want to look through this table,
and I'm going to use a different tool this time.
I'm going to use multivariate.
If I select that,
this allows me to basically look at the correlation
between all the combination of factors that are in my data table.
I'll select everything that I measured
and I'll add it in the Y columns and just hit OK.
This generates my multivariate.
The first thing I see is this table here where I've got all the correlations
for all the pairs of combinations of the factors that are put in my table.
I can see there are some pretty nice correlations here.
I'm seeing some fairly strong correlations,
but it's a little bit difficult to go through all this,
a bit overwhelming to go through all this and pick out any interesting patterns.
I've also got my scatter plot here,
and if I add a fit line to these scatter plots,
again, I'm seeing some fairly strong correlations,
but still I think this is a bit overwhelming to dive straight into.
The tool that I like to use to start with here is pairwise correlations.
If I select that, this generates a new table where I've got
all the possible pairs of variables and it's giving me the correlation.
I can sort this table based on any column.
I'm going to sort by the significant probability
and I'll make it a scending because I want
my low significant probabilities to be at the top of my table.
Then if I hit OK, I can see the first and strongest correlation I get,
in fact, involves this Flexibiliser Resin 4
that was giving us this interesting behavior.
I can see a strong correlation with the secondary or TG2.
This is a glass transition temperature.
The glass transition temperature is a temperature at which a coating changes
from being a glassy hard material to a soft rubbery flexible material.
My Flex4 level is correlating with here
a secondary glass transition temperature that I'm measuring.
And I can see also if I go a little bit further down,
my primary glass transition temperature,
the main glass transition correlates strongly with the corrosion.
S cientifically, I think they're interesting observations.
What I did based on that is I also built predictive models
for my primary TG and for my secondary TG.
Now I can look at my profiler,
but I can include all of my four predictive models.
Now I'll include the two I did before, flexibility and corrosion,
but also my primary TG and secondary TG.
Now what I can see is that the first two rows
are exactly what we were looking at before.
If I look at my primary TG,
I can see whatever I do in terms of adding new resin.
For example, if I add more of my corrosion resin,
I'm increasing my primary TG,
and that's correlating with an improvement in corrosion.
The flexibilising resins, if I add more of those,
I'm decreasing my primary TG and making my corrosion worse.
That primary TG does seem to correlate, as the multivariate is showing,
correlate very well with corrosion.
If I look at my Flex4 resin, it was having no effect on corrosion
and it's having no effect on my primary TG,
so it's different from my other flexivising resins,
but I can see for my secondary TG,
as I add more of my Flex4, it's rapidly decreasing the secondary TG.
The other resins really don't have much effect on secondary TG.
What does that mean?
What can I learn from that?
Well, any material that has multiple TGs, glass transition temperatures,
it's usually a sign that it's a multi-phase raw material.
It's not a homogeneous material.
That was the case here when we did some microscopy.
What we saw was our coating had
a continuous phase shown by this gray material here,
but it had dispersed in that a secondary phase.
The primary glass transition temperature
was correlating with that primary continuous phase
and the secondary lower glass transition temperature
was correlating to this secondary phase that we have here.
We had a hard glassy primary phase and then a soft rubbery secondary phase.
Why that's important is
usually high glass transition temperature does lead to better corrosion
because it inhibits the diffusion of anything through this layer
and stops material getting to the substrate,
the metal substrate, and causing corrosion.
Usually, if I want to make flexibility better,
I have to make this continuous layer softer
and that degrades corrosion.
But with this type of morphology,
I was able to keep my hard continuous phase
and gain flexibility through a separate dispersed rubbery phase.
This meant that anything that wanted to diffuse through the coating
and cause corrosion was always having to diffuse through this high TG area.
It's given me the combination
of good corrosion and good flexibility together.
The auxiliary data that I gathered was really responsible...
The analysis to that was responsible
for the learning of what was going on in this system.
In conclusion,
it's definitely possible to carry out successful DOEs
where we only measure the critical responses, the big Ys.
But I hope I've shown that including carefully selected auxiliary responses,
little Ys can often be really valuable, can bring clarity to unexpected results,
and it can help us to build scientific knowledge.
I hope I've also shown that JMP provides some tools that really help us with this.
I've shown a couple, but there are many more that are available.
I'd finally like to finish off by thanking the many associates
at PPG's Coatings and Innovation Center who contributed to this work.