Composites and Cements:

The materials that we are using in dentistry come from a variety of different elements. A general
classification would include metals, ceramics, and plastics. These three general groups of materials account
for almost everything you see around you. There are other naturally occurring materials, and wood is an
example, but metals, ceramics, and plastics are the materials that are used in dentistry.

Cements: Cements have been used for approximately six thousand years. However, cements do not last for
too long.

Metals: Metals have been used for over ten thousand years. They have very little use, unless they are
combined with something else. We never used metals as metals, we use them as alloys. Even gold is soft in
its pure form. There were alloys ten thousand years ago, and ancient civilizations learned to use these in a
very sophisticated way. Silver amalgam is an alloy to metals.

Plastics: Plastics are very young compared to other elements. They are cheap because they are byproducts
of the petroleum industry. Natural gas and oil are two sources for plastics, which are polymers by nature.
More recently plastics have become a very important entity for dentistry. The most important entry of
plastics into dentistry came with croat. This is a plastic material that, like most plastics, is a polymer that
polymerizes at room temperature, allowing you to mold the crown.

Ceramics: Are used to make crowns that look like tooth enamel.

Acrylics: have had a tremendous impact on the ability to make temporary crowns, bridges, and full
dentures for edentulous patients. Before acrylics dentures were made from a different polymer called
rubber. The ability of acrylics to be molded easily at room temperature, and give it color like tooth color
changed dentistry. Acrylic was also utilized as a filling material, although it failed tremendously initially.
One of the problems is shrinkage, because it undergoes a phase change, creating a double bond, resulting in
shrinkage. Ethyl is the material that you see here, and it is a gas. The material that you see here is a polyac.
We went from a gas to a solid. What I am confusing you with is a structure of a molecule, to the interatomic
distance which is irrelevant. The intermolecular distance is much further in the polymers, that is the main
reason. The acrylic is a liquid and as it polymerizes into solid, it shrinks by 20%. For this reason they are
not good materials.

Therefore, in order to counteract this, we use several thin layers in such a way that we would apply a
very thin layer, shrink and apply another layer… and so on. This technique has been used for a long time,
because the shrinkage occurs at small increments. Although we found a way to compensate this, we are still
in trouble because acrylics do not have good mechanical properties or compressive strength, and the
restoration is subject to all kinds of mechanical stresses. It has even more deficiency with physical
properties, temperature expands many things, and this is called Coefficient for Thermal Expansion, which
is 10 ppm for teeth. This means that when an individual drinks a cold drink, the tooth is going to shrink and
there will be micro leakage. Dentistry had to develop a direct filling material that could do the job without
creating leakage. Metals are not good for anterior teeth because they do not look like tooth structure.
Another possibility is to use ceramics, but you cannot make a filling out of ceramics unless you take the
impression of the tooth and send it to a lab. It cannot be used as direct filling. So dentistry came out with
composites.
Composites: came out to fulfill a mission that was not fulfilled by anything else. Dental composites are
even younger than plastics in dentistry, and came out less than 30 years ago. Composites have been around
before dentistry and have been used in areas such as sports, sailboats, airplanes, cars, etc. Composite
restoratives are a development of dentistry, but the principles of composites is something that has been
around for a long time. This is a high tech material, even jets are made out of composites, for it is a very
durable material, although not as durable as gold.

It is so much easier to restore teeth in our days due to composites. The first amalgam used was
problematic, because it was used with selant cement. There was a demarcation line between the restoration
and the tooth. It did not have good mechanical nor physical properties. The only good option for a tooth
would be to make a crown. Acrylic was always a very attractive proposition. Dentists tried to modify
acrylic, but the success rate was not tremendous. There is a problem with the material that has a
discrepancy of the properties, creating opening and closure of a space in a cyclic way, causing micro
leakage. This phenomenon is called Proportion of Liquids.

In the late 1960’s, researchers worked on a solution to use plastics in the mouth because we can
easily mold it, it sets quickly, and we can polish it. If we could only make it strong and change the thermal
properties, we could get the material to be much more helpful. In order to accomplish this goal, dentists had
to turn to composites. Composite is a general term for a group of materials used in the industry, not only in
dentistry. Composites are made of more than one kind of material. This is not new because alloys are the
combination of two metals, ceramics are the combination of building blocks, and so are plastics, but if you
take a plastic, or alloy and try to combine it with a ceramic, you can create a composite. Composites are a
combination of different materials, two or more that are dissimilar in terms of properties, that
generates another material as a result of the combination, that has properties that are different from
the properties of the components.

An example of how to create a very simple composite is an ocean storm that causes beach erosion.
People protect their homes by creating a wall of sand bags filled with sand. This is a combination of two
materials that creates a different material. Unlike alloys, components maintain their own phases in a
composite, without going into reaction. When you combine component A with component B, and create a
composite, if you do structure analysis, you can still find the components though the material is already a
composite. This is the same with the sandbags. After the storm you can still separate the sand from the
bags. In dental composites we have a combination of plastic and a ceramic particle. This combination
creates the composite properties. Ray Boen (remember this name) put together a special resin and made it a
composite for dentistry. It was a combination of plastic that was filled with a filaproctical, which happened
to be of a ceramic nature, and it created an inventorial that had the benefits of plastic, combined with the
benefits of a composite, which makes the material closer to what we want to see in teeth. What was unique
to Ray Boen’s discovery is that he identified a polymer called DIS GMA. It is a reaction product of a
material called Disphonol A, and another material called Lissitle metacroli. They together react to produce
this resonance formula. It is a very thick monomo, with a molecular weight of 504, and then it polymerizes.
Since this is too thick to work with, Ray Boen diluted it with another resin that has a lower molecular
weight called TEGDMA. These two combine and polymerize together forming a copolymer. They co-
polymerize around the small hard particles. Ray Boen was using folks, a naturally occurring mineral crystal
which is very hard. Diamond is the hardest mineral known to man. Folks is also a hard mineral, and it is so
hard that it can actually affect the opposing teeth. When this was put together we came up with a material
that all of a sudden had products that were much superior to those of a crobe.

The chemical makeup of folks is silicone dioxide, and that is what the sand in the beach is made of.
On one hand we have ceramic, on the other hand we have plastic. They don’t seem to belong to each other ,
now we want the particles to be held in the plastic matrix relatively tight, and in order to do that we need a
coupling agent. Silet is a liquid that has affinity for plastic. Silets are molecules that are basically resins
that also have an end to them which are silicones that also have affinity to ceramics. So, a dual affinity
material such as silet is a coupling agent in the filling particles. In reality, what the manufacturers do is they
take the filet particle and put it with a bait of silet, so the filet particles are coated with silet, or silinated, and
then they are introduced with the plastic and mixed together, and this creates a paste, which is then used by
us as a composite. If you look at the coefficient expansion of several materials, acrylic resin is 95 ppm/C,
while composite resins are 30 ppm/C. So it is 1/3 of the shrinkage that you get from acrylic, which is a
tremendous difference.

The material used previous to composite resinal, silicate cement, and I do want you to remember
this, because although silicate cements are not used in our days, there are other products that relate to
silicate cement. Silicate cement were the tooth colored direct restorative materials used in the 1050-1970’s
by many dentists, so you might still find patients around that have silicate cement. The coefficient of dentin
and enamel are between 7 and 12.

Acrylic is deficient primarily in compressive strength compared to composite resin, which is about
three times as strong as acrylic. In terms of shrinkage, the volumetric shrinkage of acrylic is 7 %. The
volumetric shrinkage of composite is between two to two and a half percent. So, composite resin does
shrink, but its shrinkage is much less than that for acrylic. How does composite shrink less than acrylic?
By introducing a philin particle to the equation. And the philin particle can be 70% of the material, or even
more. What happens is that by introducing the component that does not shrink you are reducing the gel
shrinkage number of the restorative material. So, just by replacing part of the resin with the ceramic we can
accomplish the 1.3 number. Although the number should be in general 2.5, there was probably a mistake
when taking this measurement. As I said, the industry is making a tremendous amount of effusive
composites and the aircraft industries was the first one, because they discovered that with composite you
can get a structural effect that is as useful as aluminum alloy, but in terms of weight, it is much less. So, in
the gray area, it is using aluminum, and in the blue area it is using a composite that is made of graphite and
epoxy (slide). This is an epoxy plastic that has graphite plastic in it, for tensile strength. This is used to
make airplanes and even jets. One of the major advantages of composite is its low weight. Aluminum is
much less surface area, but weights much more than composite. So we are learning a lot from other
industries. As they get the composite more sophisticated, it has an impact in dentistry. One day we will be
able to make partial dentures and implants out of composites.

The bonding element of composite is something that was also researched even before 1967. The
researcher, Michael Boracle (Boston, Tufts University) came out with a system called acid etching. He
found out that the citric acid which was being used in the old days would penetrate into the enamel rods and
eat away or etch the enamel in a different way. He discovered that enamel is a naturally occurring
composite, because it has an organic matrix that gets filled with inorganic material, which is hydroxyl
appetite. This fact makes it possible for the acid to etch only hydroxyl appetite and leave the areas that are
more organic in nature un etched, allowing the surfaces that are more irregular to accept a material such as a
resin that can flow into the irregularities, set there, and then to that resin we can add an additional resin on
top that contains the phyla particle, namely the composite. The composite is made from the same material
that was allowed to flow into these defects, and this is the phenomenon of bonding to enamel.

This phenomenon has produced two things:

1. A way to bond to tooth structure without mechanical retention. We get retention with amalgam by
making an undercut of the preparation. This is a rude way to keep something in a tooth. This is
created in micro mechanical interlocking that produces bonding.
2. This bonding is good for retention as well as an excellent sealing. We don’t get micro leakage
because the enamel seals.

When you acid etch enamel, it has different etching patches, classified as type I, type II, and type
III. In type I you see the honeycomb formation. Type II is when what sticks out is the middle of each rod
in the honeycomb. Type III is what you get primarily in primary teeth, and does not have a specific shape.
Most teeth (60% of the time), you get type III which is amorphous. It is not as pretty as the other types,
though. All three of them are able to accept the resin penetration, which will give the material good sealing
effect and retention. It took 15 years for dentistry to accept Dr. Boracle’s discovery, and another 15 years
for the process to be utilized widely. Bonding has lead to the inclusion of the use of composites in dentistry,
so that we can use it in dentistry as we were never able to use it before.

Strain curve – used for testing materials empirically in machines. This curve is analyzed in order to obtain
all kinds of knowledge about a material, when comparing two or three materials. If you look at this curve
you will see a comparison of materials A, B, and C, and you can see that in every one of these materials,
where the curve ends, or where the material finally broke, this connotes the ultimate strength of the material.
In this particular case, it could have been the tensile strength, in tensile strength tests. The ultimate strength
is read from the stress coordinator, because the stress coordinator is where you read how much force was
applied to what kind of surface. So, because strength is a measurement of force per area, this is where you
read it. For all these materials there is also PL (proportional limit). Up to that proportional limit there is a
proportion between the stress and the strain that is shown beyond the stress, but the strain can change a great
deal. If you look at the three materials, the PL is not the same as the UTS (Ultimate Tensile Strength) for
materials A and B. In material C, the PL and UTS are in the same point. This tells you that it will break
right off the proportional behavior, meaning that material C lacks plastic behavior. It is a brittle material. A
material that is not brittle has ductility to it. If you look at ductility of material A, it has great ductility,
therefore it is metal. After stretching it to its spring like property, which is the proportion limit, we can bend
the metal and work with it, assuming it is a metal wire, we can stretch, and flatten it because it has a lot of
ductility. Material B is not as strong as material A and does not have much ductility either. This is an
aluminum wire, which springs up to a certain point and then it can be ductile, but it is not as good, thus
breaking off the wall. Material C is more like a rubber wire, which is easy to stretch and has low force, and
then it snaps off because it is brittle and has no ductility. It has elasticity but no ductility. Here is another
depiction of how you can find ductility in a stress strength curve. Read the chapter in the book that talks
about stress strength curve.

Physical property is another property that is called surface phenomenon. If we take a drop of liquid
and put it over a solid, that drop of liquid may have different configurations. This is one configuration of a
drop of liquid. The liquid creates a saucer shape over the solid. We can put this in a special instrument and
measure the angle that the liquid forms with the surface. This angle changes with different liquids and
different surfaces. In another liquid, or another configuration you will see a different angle. The surface
that has a low surface energy does not like to accept the liquid, while the high surface energy allows the
liquid to adhere to it quite easily. When teeth are dirty, additional plaque will adhere to them. A clean,
brushed, and polished teeth with fluoride paste is smooth and additional plaque does not want to adhere to it.
This is a surface phenomenon that connotes with wreathing. When you have a small angle like this the
surface is wreathed, but as the angle becomes larger, the surface is not wreathed at all. The correlation of
this to bonding is that enamel has usually a low surface energy, so that a bonding agent will not want to
bond to the enamel. What we are doing though, instead of changing the bonding agent, we are acid etching
it. Acid etching is the reverse of polishing it. So the acid etched enamel is good working. The angle
changes and the material can sustain on the enamel. Remember that surface wetting occurs due to surface
energy, or surface tension. Surface energy is something that relates to solids, surface tension is something
that relates to liquids, but they are interchangeable. The amount of surface energy or surface tension will
dictate how much wetting will occur between a liquid and a solid. Another thing that will dictate that is how
much the two items like each other. When the liquid is water or water base, the surface will dictate how
much the water will adhere to it, because we have surfaces that are hydrophilic or hydrophobic. So, an
impression material or other items can accept water easily or reject water.
Cementation:

Adhesion is a phenomenon that relates to an adherence and an adhesive. The phenomenon involved in the
two plates of glass mentioned above is adherence. We are trying to adhere them to each other. If these two
glass plates were perfectly smooth, and I placed them on top of each other, they would adhere. Even if they
were not smooth they would have some kind of surface tension, and they would attach to each other. If the
surfaces were perfectly smooth, and I put them together they would become one item, and that is because if
the surfaces were perfectly smooth, the distances between the molecules of one plate and the molecules of
the next plate would have the same distance as they have within the plates. If I can bring a situation to
having the intermolecular distances between molecules in plate A and plate B to be the same distance as
they are within the plate, then this would become one material. The reason I can’t do that is that we in
reality have no means to polish a surface to be looking totally flat and totally smooth. So if I look at the two
plates under the microscope, it will reveal that the intermolecular distance is not what I was hoping it to be,
because the plate A which is on top and plate B which is underneath meat each other through all kinds of
irregularity, although to the naked eye the surface may look perfectly smooth, they are still not absolutely
straight. This does not exist; therefore I cannot bring it to adhesion simply by putting them on top of each
other. There will be some attraction between them, but it is barely enough to keep them adhere. I can do
something to cause adhesion by putting water in between them, and the intermolecular distance will be
smaller. Water needs to solidify in order to really adhere to the surface. So I put it in the freezer for 30
minutes, and when I take it out you won’t be able to separate these two plates, that is how strong it is going
to be. So, adhesion depends on an adhesive that is really running onto the surface of each adherent, filling
up the surface well, and then solidifying. However we do not have many materials that do it well. The
materials that you use are not going to wet well and air will be entrapped, and good adhesion will not be
created. Another problem is that the adhesive does not solidify.

Cementation is some kind of adhesion in the oral cavity, where we adhere a structure that we have
created to a structure that is the tooth, which is underneath. We are using eluting cements in dentistry for
retention of the restoration and also for filing the gap of the space between the restorations of the tooth. We
cannot allow a crown, a relay, or a bridge to have any kind of space between the tooth and the metal,
ceramic or plastic. In general, the dental eluting cements that we use are characterized by three groups: one
is the conventional cements, which are acid base materials: combination of acid and base. They are also
called water-based cements because the acid always contains water. We have 2 new groups of cements
which are called the high bridge or resin modified cements, this group has been around only for four or
five years, and then there is the resin cements which relate to composites. All the resin cements are the
same as composites except that they have a lower degree of filter particles, and the resin cements are more
flowing. We utilize these cements according to the specific situation in the oral cavity that needs the
cement. Here are two anterior crowns that are going to be cemented. One crown is cemented to a tooth that
had a root canal treatment, and then the root canal treatment necessitated a composite build up. When the
crowns go on, they are cemented to different cements because there is a certain cement that they use to these
kinds of applications and another one that they cement to metal. This is why it is so important to understand
what cement to use in what situation.

Cements are very important to understand and new cements can do what older cements could not
do. The conventional cements include primarily three cements: Zinc phosphate cement, which is cement
that we have used for many years. It is a good cement because when you use the acid and the base, it
creates a paste, and that paste can be placed on the crown and the crown can be placed on that tooth. The
paste has a low viscosity, so you can sit the crown all the way down, and after a few minutes the cement that
is in between the crown and the tooth will set and will become a solid, and that solid interlocks the crown
into the dentine. It doesn’t do it by adhesion. What happens is that as the cement is placed in the crown, it
is like a liquid, runs into the surface and becomes a solid that interlocks the dentine for thirty or forty years.
It has some deficiencies though, and one of the deficiencies is that it is water-soluble, so that in the mouth
saliva can eat it up and it can become a problem. That can take a long time, and we counteract this by
having crowns that have margins that actually close down to the dentine so that the cement is almost
unexposed. But in some situations, in the long run, this can create some problems. The fact that the cement
can give up due to the fact that it is soluble will allow the cement to degrade under the crown, and bacteria
will set in, and secondary caries will develop and erode under this margin, causing the cement and the
crown to fail. So we need cement that is not soluble. Zinc phosphate is soluble and does not adhere to the
tooth.

Another cement that is very similar to Zinc phosphate is the polycarboxy cement. In both of these
cements, the parder is zinc oxide. When you oxidize zinc it looks white. The zinc oxide parler is basic in
terms of pH. If we mix the parlor with a liquid that is an acid, the acid will activate, and will create a paste
that will solidify by a reaction of the base and acid. The acid of zinc phosphate is phosphoric acid, which is
inorganic. The acid with this cement is poly acrylic acid, an organic acid. The organic acid gives the
cement an advantage in the fact that it makes it adhere to the tooth structure. Therefore, cements have gone
an evolution. We started with one cement and tried to improve it. The third conventional cement is called
glasseiano cement. (Read the chapter in your text and identify the differences between these two cements).