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Crystalline Polymer

To understand crystalline polymers, I suggest you go home (if you're not already there). Now I can already imagine the confused look in your eyes. Home? Why would I need to go home? So you can check your sock drawer! 

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Crystalline Polymer

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To understand crystalline polymers, I suggest you go home (if you're not already there). Now I can already imagine the confused look in your eyes. Home? Why would I need to go home? So you can check your sock drawer!

You see some people are very clean and tidy. When they put the socks in the drawer they fold them and put them away in an orderly way. Others however aren't. There are people who are not very interested in the cleanliness and order of their sock drawer. These guys are just going to throw their socks in the drawer and leave it messy.

Polymers are like socks. Sometimes they are arranged in an orderly manner, like the socks in the drawer of people who need everything to be ordered. In this case, the polymer is called crystalline. Other times there is no order, and the polymer chains just form a big tangle like the socks of those who are messy. When this happens, the polymer is called amorphous.

In this article, we will discuss what crystalline polymers are all about, their properties, structures, examples and different types!

  • This article is about crystalline polymers.
  • Crystalline Polymer Definition: defining what crystalline polymers are.
  • Crystalline Polymer Properties: Explain the properties of crystalline polymers.
  • Crystalline Polymer Structure: explaining the shape and composition of crystalline polymers.
  • Semi Crystalline Polymer with Examples: providing real-life examples about semi-crystalline polymers.

Crystalline Polymers Definition:

Fun fact: not a single polymer is completely crystalline because all crystalline polymers contain considerable amounts of amorphous material. Therefore, crystalline polymers are more accurately called semi-crystalline polymers.

How can we define crystalline polymers then?

Crystalline polymers are polymers in which some parts have crystallized in a precise order, allowing the formation of an organized solid unit.

Remember, although it is possible to create a 100% amorphous structure, it is impossible to create a 100% crystalline structure as crystalline polymers always contain a decent number of amorphous polymers.

This can be seen in the figure below, which clearly demonstrates how materials and elements are always characterized by the presence of an amorphous element:

Crystalline & AmorphousFig. 1: Crystalline + Amorphous in the presence of an element: https://support.3devo.com/oval-flat-shaped-filament/

Pretty standard so far no? Let's find out about its properties!

Crystalline Polymers Properties:

Due to their structure and temperature, crystalline polymers have a wide range of mechanical and physical characteristics:

  • High density.
  • High melting point.
  • High resistance to wear and tear.
  • Low ductility and impact resistance.
  • Opaque to visible light.

The biggest characteristics of crystalline polymers are: high melting point, rigidity, and resistance to solvent penetration. Although the crystallinity makes polymers robust, it also lowers their resistance to impacts.

Crystalline polymers furthermore exhibit x-ray diffraction patterns due to the existence of specific lattice patterns of molecules in polymer chains and exhibit a crystalline melting temperature. X-ray diffraction, density measurements and heat of fusion are measured to determine the fraction of crystalline substances present in a particular polymer.

X-ray diffraction (XRD - X-ray diffraction) is an analytical technique that provides information on the identification of the structure and phase of crystalline materials.

On a general spectrum though, all of the properties of the semi-crystalline structures mentioned above are conditional to the degree of crystallization, to the structure of the lamellar crystallites (tiny, alternating layers of various materials), and to the size and distribution of these structures.

crystallite means an individual single crystal.

Crystalline Polymers Structure:

Crystalline polymers are characterized by a three-dimensional order. Now, assuming as a general rule that all molecules have a certain structural regularity, the molecules in the structures of crystalline polymers are for the most part aligned parallel to each other.

As we learned above concerning the properties of crystalline polymers, these structures can crystallize under certain conditions of temperature, pressure, voltage or by the influence of a medium, adopting fully extended forms (such as helical forms for instance).

X-ray diagrams have revealed the existence of two different parts of the structure of a crystalline polymer: an interfacial amorphous one and an ordered crystalline one, giving rise to the existence of a micellar pattern.

  • The ordered crystalline regions are formed by sequences of the polymer chains in ordered conformations.
  • The interfacial region is determined by the re-entry of a part of the chain into the crystallite.
    • the amorphous region is characterized by parts of the chain in disordered conformations (as amorphous polymers are disorderly).

Take a look at the image below to have a visual representation of what was explained above (notice how they are all aligned parallel to each other too):

The lamella of a polymer crystal is made up of closely spaced and folded polymer chains (loops) that take on a mostly planar zigzag and helical form.

Crystalline Polymers StructureFig. 2: Structure of crystalline polymers: crystalline region vs. amorphous region https://www.victrex.com/en/blog/2017/polymer-crystallinity-hpp-explained-part-

Semi-Crystalline Polymers with Examples

Examples of crystalline polymers are, but not limited to:

  • Polyethylene (PE), Polypropylene (PP), and Polybutylene terephthalate (PBT)
    • Polyethelyne (PE) is an element we use on a daily basis (and arguably the ruin of our environment). PE is the most common plastic.
    • Polypropylene (PP) is a plastic as well.
    • Polybutylene terephthalate (PBT) is a type of polymer used mainly in the engineering field - mostly as an insulator in the electric and electronic industry.

Now, all of these are just super long words that aren't super important, unless you are working with them daily. However, they are super cool because these types of materials are commonly used in the field of dentistry!

Dental Repairs using PolymersFig. 3: Polymers used in chipped tooth repair: https://www.drjamescovan.com/treatment/cosmetic-dentistry/chipped-teeth

Semi-Crystalline polymers have mostly been used to build prosthetic items like denture bases. However, they are also employed in endodontic fillings, prosthetic teeth, restorations, cements, elastics, inlay patterns, implants, impression materials, and many more!

Look at the image here: notice the chipped teeth and then how they were fixed after bonding? The material used for bonding has a high quantity of polymers in it!

What about the polyethylene that we mentioned above? Given that it is one of the strongest currently available reinforcing fibers they are great for cosmetic dentistry as they have low density and modulus, are formed of matched polymer chains, and have high impact resistance.

Crystalline Polymer - Key takeaways

  • Crystalline polymers are polymers in which some parts have crystallized in a precise order, allowing the formation of an organized solid unit.
  • Although it is possible to create a 100% amorphous structure, it is impossible to create a 100% crystalline structure as crystalline polymers always contain a decent number of amorphous polymers.
  • Crystalline polymers have a wide range of mechanical and physical characteristics:
    • High density.
    • High melting point.
    • High resistance to wear and tear.
    • Low ductility and impact resistance.
    • Opaque to visible light.
  • Crystalline polymers are characterized by a three-dimensional order and the molecules are aligned in a parallel manner with each other.
  • There are two different parts to the structure of a crystalline polymer: an interfacial amorphous one and an ordered crystalline one, giving rise to the existence of a micellar pattern.
    • The ordered crystalline regions are formed by sequences of the polymer chains in ordered conformations.
    • The interfacial region is determined by the re-entry of a part of the chain into the crystallite.

Frequently Asked Questions about Crystalline Polymer

Crystalline polymers are polymers in which some parts have crystallized in a precise order, allowing the formation of an organized solid unit.

Examples of crystalline polymers are, but not limited to: 

  • Polyethylene (PE), Polypropylene (PP), and Polybutylene terephthalate (PBT) 
  • Semi-Crystalline polymers have mostly been used to build prosthetic items like denture bases. However, they are also employed in endodontic fillings, prosthetic teeth, restorations, cements, elastics, inlay patterns, implants, impression materials

The difference between crystalline and amorphous polymers is that while amorphous polymers are solids whose molecular chains are arranged in a disordered way in space, crystalline polymers are polymers in which some parts have crystallized in a precise order, allowing the formation of an organized solid unit.

Crystalline polymers

  • High density. 
  • High melting point.
  • High resistance to wear and tear.
  • Low ductility and impact resistance.
  • Opaque to visible light. 
  • High energy.

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