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nGen Colorfabb

> Chemical composition and synthesis

Colorfabb nGen is composed of Eastman’s Company Amphora AM3300,  which is a copolyester with similar composition to PETG [1]. The exact chemical ingredients of this type of filament however remains a well guarded secret, and therefore this section will relate what is known about PETG.

 

Polyesters are thermoplastic polymers with a linear chain and ester groups within the polymer backbone. The first polyester to be synthesized was PET, which stand short for poly(ethylene terephthalate). PET is made of ethylene glycol (EG) and terephthalic acid (TPA) or dimethyl terephthalate, depending on which process is used. If the acid is used, PET is produced through an estirification reaction while the dimethyl terephthalate involves a transesterification. Both processes however result in the same structure, as represented below. [2]

Image from wikipidea.com

Image from lulzbot.com

> As printing material

A very thorough review of nGen Colorfabb was written by the 3dprintingforbeginners.com website [5].

Colorfabb nGen has a larger print window than PETG, despite their similar composition. The processing temperature can range from 210°C to 240°C. Although the Eastman datasheet indicates a heated bed temperature of 60°C, the nGen website advises a heated bed of 75°C-85°C, meaning close but just below the glass transition temperature in order to allow the material to solidify upon cooling. If the bed was heated above the glass transition temperature, the material would remain in its viscous state. [6]

Colorfabb nGen was created in order to solve all the drawbacks of the conventional 3D filaments: the brittleness of PLA on one side and the odor of ABS emitted during printing and the high risk of warping on the other side.

If printed at the correct settings (which can be found on the nGen How to print page [6]), the warping should be minimal or even non existent. Other advantages of nGen are excellent flow properties and easy printing. Colofabb nGen also give good results with overhangs. The best feature is the high quality surface finish of the printed pieces.

PETG, which stand for Poly(ethylene terephthalate) glycol-modified, is a PET modified by copolymerization with cyclohexane dimethanol (CHDM). This means the cyclohexane dimethanol partially replaces the ethylene glycol in the PET backbone, resulting in a the addition of more carbon atoms as the (CHâ‚‚)â‚‚ is replaced by a cyclohexane. PETG synthesis occurs through a two-step process: first the esterification of TPA, EG and CHDM in presence of a catalyst, followed by the catalysed polycondensation of the first reaction products. PETG copolymers can have varying compositions and microstructures. The addition of cyclohexane reduces the crystallinity of the polymer through the reduction of the molecular regularity. [3]

[3]

> Properties

All the properties of Amphora AM3300 are listed in the datasheet published by Eastman Company. Overall the mechanical properties are in the same range as its filaments rivals like ABS or PLA, with a tensile strength of 50 MPa at yield. It can elongate up to 193% before breaking. Furthermore, Amphora AM3300 has a density of 1.2 g/cm², which although heavier than ABS, remains on the lighter side of all available filaments. A final property which is praised by Eastman company is that Amphora AM3300 is styrene-free, as styrene is considered to be a hazardous material. [4]

Like PETG, Amphora AM3300 is an amorphous thermoplastic with a glass transition temperature at 85°C, which is significantly higher than the conventional 3D printing filaments like ABS or PLA. It is also more heat resistant than PLA. [5]

> Applications

Colorfabb nGen is said to be an all-around filament, meaning it can have a wide range of applications. Although not as tough as ABS, it still has good mechanical properties. It can also be used for applications for which heat resistance is required. However, nGen Colorfabb is best used for applications where the aesthetic aspect of the object is important. 

[1] “30 Types of 3D Printer Filament – Guide & Comparison Chart”, https://all3dp.com/best-3d-printer-filament-types-pla-abs-pet-exotic-wood-metal/#ngen, accessed on 12/03/2017

[2] Herman Mark, “Encyclopedia of polymer science and technology: plastics, resins, rubbers, fibers, Volume 7”, 2007, 504-521

[3] T. Chen, G. Jiang, G. Li, Z. Wu and J. Zhang, “Poly(ethylene glycol-co-1,4-cyclohexanedimethanol terephthalate) random copolymers: effect of copolymer composition and microstructure on the thermal properties and crystallization behavior”, RSC Adv., 2015,5, 60570-60580

[4] Eastman Company, “Technical Data Sheet: Eastman Amphora™ 3D Polymer AM3300“, https://www.lulzbot.com/sites/default/files/AmphoraAM3300-TDS.pdf, accessed on 12/03/2017

[5] “What Material Should I Use For 3D Printing? – Advanced Materials Review #5 – nGEN from ColorFabb”, http://3dprintingforbeginners.com/colorfabb-ngen-review/, accessed on 12/03/2017

[6] Colofabb, “How to print with nGen”, http://ngen.colorfabb.com/how/, accessed on 12/03/2017

[7] Hay, J. N., “The physical ageing of amorphous and crystalline polymer”, Pure & Appl. Chem., Vol. 67, No. 11, 1995,  pp. 1855-1858

[8] Richard P. Chartoft, Anil K. Sircar, “Thermal Analysis of Polymers”, Encyclopedia of Polymer Science and Technology, 2005

​[9] Nicola A. Bailey, James N. Hay, and Duncan M. Price ,”A study of enthalpic relaxation of poly(ethylene terephthalate) by conventional and modulated temperature differential scanning calorimetry”, Proceedings of the 27th conference of the north american thermal analysis society, september 20-22, 1999, Savannah, Georgia, http://citeseerx.ist.psu.edu/viewdoc/download?doi=10.1.1.424.7183&rep=rep1&type=pdf

> Bibliography

> Experimental characterisation

The test printing consisted of printing out a standard dogbone shape. The printer settings were fixed as followed

  • Extrusion temperature of 230°C

  • Heated bed temperature of 80°C

  • Print speed of 40 mm/s outlines and 90 mm/s for infill

The printing bed was covered with blue tape and the dogbone was printed with a breakable support.

The resulting dogbone is visible on the picture below.

>> Printing test

Overall the printing with nGen Colorfabb was quite straightforward. The promise of good flow properties seemed true at first glance, but rheometry measurements will be performed in order to verify this. The printing is easier than with ABS as there is no warping involved and the material correctly adheres to the blue tape. The shiny finish of the printed object makes it quite aesthetic.

>> DSC

The nGen filament was dried overnight at 60°C before performing the DSC. The measurement was performed using around 5 mg of the polymer, sealed in a aluminium pan. The sample was heated to 300°C with an average rate of 10°C per minute.

From the given properties of the data sheet [4], one would expect a heating curve that remains flat except for a shift in the baseline at 85°C, which characterizes the glass transition temperature. However, the obtained curve after DSC is quite different.

On the resulting heating curve, there were three peaks that characterise endothermic transitions. One around 30°C, one at 87°C and one at 207°C. As a phase transformation slightly above room temperature seems unlikely given the polymer properties,  the first peak was considered as an artefact linked to the onset of the DSC, and thus erased from the DSC curve .

 

The second peak is quite interesting: at this temperature, one would expect to see a glass transition, but it is not apparent at first sight. However, when one extends the baselines at both edges of the peak, a shift appears: this is the glass transition. The endothermic peak that follows the glass transition characterises an enthalpic relaxation [7]. The material was dried overnight at 60°C (which is close but still below Tg) and then left to (slowly) cool in desiccator for several hours: this can be assimilated to physical aging the material. Upon aging, the enthalpy progressively decreases. Indeed, when an amorphous material is in its glassy state, it is in non-equilibrium froze liquid like state with an excess of thermodynamic properties like enthalpy and volume. When held close but below Tg for a long time, this non-equilibrium glass tries to attain a lower energy equilibrium. Physically, the polymer chains, which still retain some mobility, will rearrange, rendering the material more brittle [9]. The dissipated enthalpy is recovered upon heating the material above Tg and takes the form of an endotherm at the glass transition [7]. The presence of an enthalpic relaxation make the precise identification of Tg difficult. However, if one draws a line between both edges of the endotherm and measures its middle, one obtains a midpoint glass transition temperature of ~85°C. This is thus as expected.


The third and last peak is smaller, but cannot be ignored (even though this peak is unexpected). This endotherm can be associated to the melting of the filament, making the material semicrystalline instead of amorphous. The melting peak is quite broad. The area below it is related to the amount of crystalline material in the polymer [8]. However, the percentage of crystallinity could not be determined as a reference value is needed. Indeed, the crystallinity of a material is obtained by normalizing the observed heat of fusion to that of a 100 % crystalline sample of the same polymer. However, such a polymers are often rare, and therefore literature value are used. In the case of nGen, as the exact composition of the material is unknown, literature values were not available and thus the crystallinity of the material could not be determined [8].

>> Rheometry

A typical rheometry measurement of the storage modulus G’ and the loss modulus G’’ for a thermoplastic in its rubbery state (so heated above Tg) with respect to the angular frequency has the following aspect.

In the measurement below, only the first increase at low frequency is represented for both measurements. This first increase corresponds to the relaxation of the polymer, meaning it flows. The first few points of the measurement of G’ at both 220°C and 250°C can be discarded as the observed value is quite low and close to the limit of the rheometer. The curve for G’ at 250°C also misses some points, but as not much information can be obtained from it, it is not necessary to do the measurement again.

The viscosity remains quite constant, indicating the polymer flows both at 220°C and at 250°C. This also means that, unlike most 3D printing materials, there is no shear thinning effect, meaning the printing speed has no effect on the flow properties of the material.

Viscosity can also be seen as the product of the plateau modulus G₀ᴺ and the relaxation time. As the plateau modulus is expected to be the same at both 220°C and 250°C (there is just a shift in the curve, like the dotted line on the theoretical curve above), one can conclude that the relaxation time decreases, indicating that the material is less viscous and thus more fluid at 250°C.


On the whole, one can conclude from this graph that Colorfabb did not lie about the nGen’s excellent flow properties. At 220°C, the material already flows quite easily. At 250°C, it is even less viscous, meaning it flows even better. Good flow properties go hand in hand with better layer adhesion. However, one must be careful because if the material is too fluid during printing, there will be a loss of precision as the material spreads out more. A compromise must thus be found. 

> Conclusion

On the whole, nGen Colorfabb would have been perfect for our applications: it has good thermal properties, its mechanical properties are similar to those of ABS and PLA and most importantly, it is print-friendly. However, only a sample of this material was available to us and it was not enough to print out the entire drone. We therefore (quite reluctantly for some of us), put this material aside and concentrated on other materials that were available in larger amounts.

By Roselien

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