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Chemical resistance of 3D printable polymers: literature review

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{{L3999 Fall2017}}
This is a literature review for a study on the chemical resistance of 3D printable polymers. This literature review is initially targeted at liquid chemicals which can "attack" 3D printed polymers. In the future gas and plasma attack can be studied but for now it is out of the scope of this lit review.
==Introduction==Our target is to find out what FFF (fused filament fabrication) 3D printing filaments tolerate the harsh chemicals that we use in semiconductor processing and other cleanroom processes. FFF was chosen as the preferred 3D printing method thanks to its versatility, cost-effectivity and relative ease. 3D printing filaments are made from plastics by using additives (plasticizers and colorants), and the vendors rarely or ever provide the information on them to the customer. Therefore, it is not guaranteed that if a certain polymer tolerates, for example, HCl, 3D printed objects made from the same polymer could be used to make custom labware. Further on, we do not know if the printing (thermoplastic extrusion) itself changes the chemical properties of the materials.
==Chemicals Polypropylene (PP) is a 3D printable polymer that can tolerate many chemicals, and processes==the authors of articles listed below have made reaction vessels and microfluidics applications from it. But are we limited to PP? In this we need to search for clues in chemical compatibility charts, also found below.
===List of chemicals===The resistance of We will experiment on 3D printable materials at least to the following solvents, acids printing filaments and 3D printed objects by testing them in different chemicals and solutions is tested:* Deionized H2O* Isopropanol* Acetone* Hydrochloric acid (HCl), 37%* Ammonia (NH3), aqueous solution 25%* Hydrogen peroxide (H2O2), aqueous solution 30%* Nitric acid (HNO3)* Phosphoric acid (H3PO4)* Acetic acid, concentratedobserving if they swell or dissolve.
These chemicals are common chemicals used in many laboratories =Sources====Journal Articles=======[https://www.nature.com/articles/nchem.1313 Integrated 3D-printed reactionware for chemical synthesis and many semiconductor processing stepsanalysis]====Mark D. Symes, such as Philip J. Kitson, Jun Yan, Craig J. Richmond, Geoffrey J. T. Cooper, Richard W. Bowman, Turlif Vilbrandt & Leroy Cronin, Nature Chemistry 4, 349–354 (2012), doi:10.1038/nchem.1313*Reactionware for inorganic and organic synthesis*Reactionware: combines reaction vessel combined with reagents, catalysts, or control of shape to produce a desired result*Printed-in : catalysts and in-situ characterization*Modifying the cleaning geometry changes the outcome of silicon wafersthe reaction*Robocasting of acetoxysilicone polymer (Loctite 5366): does not require heat, the material hardens quickly.*The properties of the material modified by e.g. mixing in conductive carbon black*Reusable reactionware, cleaved reactor could be glued shut again with the same material after cutting it open
===Chemical processes=[http://pubs.rsc.org/en/Content/ArticleLanding/2012/LC/c2lc40761b#!divAbstract Configurable 3D-Printed millifluidic and microfluidic ‘lab on a chip’ reactionware devices]====Philip J. Kitson, Mali H. Rosnes, Victor Sans, Vincenza Dragone and Leroy Cronin, Lab Chip, 2012, 12, 3267–3271. DOI: 10.1039/c2lc40761b*Resist stripMillifluidic devices, made using PP (FFF, 3DTouch printer)*RCA1 Properties of PP: robust, flexible, chemically inert, low cost*Three different millifluidic devices were made and RCA2 wafer cleaning processesdemonstrated*Containers for solid materials were filled during printing and the printing was continued, which sealed the containers*Time and cost-effective method compared to traditional methods, single device takes only hours to build*Future interest: solvent compatibility
====[https://www.beilstein-journals.org/bjnano/articles/4/31 Continuous parallel ESI-MS analysis of reactions carried out in a bespoke 3D printed device]====
Jennifer S. Mathieson, Mali H. Rosnes, Victor Sans, Philip J. Kitson and Leroy Cronin, Beilstein J. Nanotechnol. 2013, 4, 285–291. doi:10.3762/bjnano.4.31
*3D printed tailored deviced linked to a mass spectrometer
*3DTouch printer used to print thermoplastic PP
*PP: low cost, robust, flexible, chemically inert
*Screw fittings made from PEEK (harder than PP), provides a tighter seal
====[http://pubs.rsc.org/en/content/articlehtml/2013/sc/c3sc51253c Combining 3D printing materials and their liquid handling to produce user-friendly reactionware for chemical propertiessynthesis and purification]====Philip J. Kitson , Mark D. Symes , Vincenza Dragone and Leroy Cronin, Chem. Sci., 2013, 4, 3099-3103. DOI: 10.1039/C3SC51253C*Reactionware for a multi-step reaction was made, step control by rotating the device and letting gravity do the work -> need for pumps eliminated*Approaches from earlier articles combined: vessel was printed from PP, liquid-handling robot was used to functionalize the vessel*PP: melting point approx. 160°C, maximum working temperature 150°C*PP impermeable to hexane and diethly ether vapors, pressure build-up might need to be mitigated ===PLA =[http://pubs.acs.org/doi/abs/10.1021/ac403397r Evaluation of 3D Printing and Its Potential Impact on Biotechnology and the Chemical Sciences]====Bethany C. Gross, Jayda L. Erkal, Sarah Y. Lockwood, Chengpeng Chen, and Dana M. Spence, Anal. Chem., 2014, 86 (Polylactic acid7), pp 3240–3253, DOI: 10.1021/ac403397r*Common FDM/FFF materials: PC, ABS, PS, nylon, metals/ceramics*Many polymeric materials absorb small organic molecules, can also absorb organic or aqueous solvents. This can results in swelling of the bulk material ====[http://onlinelibrary.wiley.com/doi/10.1002/anie.201402654/abstract 3D Printed High-Throughput Hydrothermal Reactionware for Discovery, Optimization, and Scale-Up]====One Philip J. Kitson, Ross J. Marshall, Deliang Long, Ross S. Forgan, and Leroy Cronin, Angew. Chem. Int. Ed. 2014, 53, 12723 –12728 . DOI: 10.1002/anie.201402654*Sealed monolithic reaction vessels from PP for hydrothermal synthesis. Array reactor, which allowed multiple experiments during one heating step.*Considerable savings achieved with 3D printed vessels compared to commercial alternatives*Another advantage: quick prototyping and ease of tailoring cheaply*FDM/FFF of PP*PP starts to soften at 150°C, some reactors burst in the most heating due to pressure build-up. Reactors were safe for aqueous/DMF solutions over 72 hours at 140°C. ====[http://pubs.rsc.org/en/content/articlehtml/2014/lc/c4lc00171k 3D printed microfluidic devices with integrated versatile and reusable electrodes]====Jayda L. Erkal, Asmira Selimovic , Bethany C. Gross, Sarah Y. Lockwood, Eric L. Walton, Stephen McNamara, R. Scott Martin, and Dana M. Spence, Lab Chip, 2014, 14, 2023-2032. DOI: 10.1039/C4LC00171K*3D printed devices, used in electrochemical detection. Printed using Objet Connex 350, material [http://global72.stratasys.com/~/media/Main/Files/SDS/Transparent-Materials/SDS-Object-VeroClear-RGD810-EU.pdf#_ga=2.176020706.1338903111.1510562312-2074105264.1508231826 VeroClear] (acrylate-based polymer).*Many electrode materials integrated in these devices for applications in e.g. detecting neurotransmitters, NO.*CADs and 3D printing filaments: custom parts fitted into commercial equipment, rapid troubleshooting, easy to share designs with others. Various vendors  ====[https://www.nature.com/articles/nprot.2016.041.pdf 3D printing of versatile reactionware for chemical synthesis]====Philip J. Kitson, Stefan Glatzel, Wei Chen, Chang-Gen Lin, Yu-Fei Song,and available in multiple colorsLeroy Cronin, Nat. BiodegradableProtocols, potentially 2016, 11 (5), 920-936*Describes the steps for making 3D printed reactionware*Open-source type development driving the growth of 3D printing*Advantages of 3D printing in chemistry: topology, geometry and composition of reactors precisely controlled*The versatility of 3DP materials is an advantage, but all of their applications impossible to describe in a single document*Extrusion-based methods (FFF/FDM) popular and economical, PLA and ABS most common materials*FDM applied in making fluidic reactors, but for the most part research focused on 3D printable materials, post-treatments, and batteries and LEDs*Limitations: epoxy- and acrylate-based materials used in SL not very resistant organic solvents or extreme pHs. Similar problems for PLA and ABS.*FFF/FDM of nylon and PP more promising for chemical applications*Perfluorinated polymers difficult to chemicalsprint (small temperature window) and toxic.*Conventional FFF/FDM materials suitable for biological labware (water solutions, mild pH)*Choosing a material: inert to the desired chemistry. The author's choice: PP. Easy to print, good resolution and chemically inert.*PP attacked by very strong oxidizers, also by heated solvents (toluene)*Different grades of PP require different print settings (different melt profiles and flow) ===Chemical resistance charts===*[http://www.fmelighting.com/pdfs/Chemical_Resistance_Chart.pdf Rosemount analytical huge chart, resistance as a function of temperature]*[https://www.curbellplastics.com/Research-Solutions/Technical-Resources/Technical-Resources/Chemical-Resistance-Chart Curbell Plastics]*[http://sevierlab.vet.cornell.edu/resources/Chemical-Resistance-Chart-Detail.pdf Thermo Scientific Nalgene Products], Cornell University Sevier lab*[http://www.ensinger-online.com/fileadmin/pictures-pdf/Download/Brochures/ENS-Stock_shapes_Chem-Resistance_14.pdf Ensinger Plastics]*[http://www.sirmax.it/sites/default/files/Chemical%20resistance%20of%20polymers.pdf Sirmax] ===Books===*Schreirs, J. [https://books.google.fi/books?hl=fi&lr=&id=08y8kcvRS6AC&oi=fnd&pg=PA3&dq=fluoropolymer+chemical+resistance&ots=S-_sDXzXtG&sig=NDvFlfAP4WyGG9tPN5C6bSzYqUU&redir_esc=y#v=onepage&q=fluoropolymer%20chemical%20resistance&f=false Modern fluoropolymers.] Scheirs, J., Ed (1997): 32.*Moiseev, Yu V., and Gennadiĭ Efremovich Zaikov. [https://books.google.fi/books?hl=en&lr=&id=8N2-fzAFw18C&oi=fnd&pg=PA1&ots=lIjOuftT7lsig=YtNNWguSLSGCe48AjzOpid_u_i0&redir_esc=y#v=onepage&q&f=false Chemical resistance of polymers in aggressive media]. Springer Science & Business Media, 1987.*Seymour R.B., Carraher C.E. (1984) [https://link.springer.com/chapter/10.1007/978-1-4684-4748-4_10 Chemical Resistance of Polymers]. In: Structure—Property Relationships in Polymers. Springer, Boston, MA.
=3D printing materials and their chemical properties=
===ABS (Acrylonitrile butadiene styrene)===
One of the most used 3D printing filaments. Various vendors and available in multiple colors. Potentially more resistant to water and other chemicals than PLA.
According to [https://www.curbellplastics.com/Research-Solutions/Technical-Resources/Technical-Resources/Chemical-Resistance-Chart Curbell plastics], resistant to following chemicals:
*Acetic acid 5%
*Acetic acid 10%
*Ammonia solution 10%
*Ethanol 96%
*HCl 2%
*HCl 36%
*H2O2 30%
*H3PO4 10%
*H3PO4 concentrated
*H2SO4 2%
*H2O cold
*H2O warm
 
Limited resistance to:
*HF 40%
*IPA
 
Not resistant to:
*Acetic acid concentrated
*Acetone
*HNO3 2% (NOTE: [http://www.ensinger-online.com/fileadmin/pictures-pdf/Download/Brochures/ENS-Stock_shapes_Chem-Resistance_14.pdf Ensinger chart] mentions that Tecaran ABS is resistant to this)
*H2SO4 98%
 
===ASA (Acrylonitrile styrene acrylate)===
[https://en.wikipedia.org/wiki/Acrylonitrile_styrene_acrylate Acrylonitrile styrene acrylate], structurally similar to ABS but with improved UV resistivity and mechanical properties. Slightly hygroscopic.
===Co-polyesters===
Commercial 3D printing filaments: Inova Co-Polyester, ColorFabb nGen. No mentions of chemical properties, not advertised as a chemically resistant material.
===PETG======PP FEP (PolypropyleneFluorinated ethylene propylene)===Resistant Should be in the sweet spot of fluoropolymers. Low enough melting point to various laboratory chemicalsbe printable but chemically very durable. Quite According to some data should be resistant to acids and bases. Widely nearly all room temperature liquid chemicals used in clean rooms. ===Nylon===[http://taulman3d.com/alloy-910-spec.html Taulman Alloy 910] is [https://www.youtube.com/watch?v=8_pt_05BqYk apparently] Nylon-based. Is susceptible to oxidation for example peroxides, advertised as it is just chemically resistant, but presumable absorbs a hydrocarbonlot waterAccording to [https://www.curbellplastics.com/Research-Solutions/Technical-Resources/Technical-Resources/Chemical-Resistance-Chart Curbell plastics], Nylon 6 is resistant to following chemicals:*Acetic acid 5%*Ammonia solution 10%*Ethanol 96%*IPA*H2O cold Limited resistance to:*Acetone*H2O warm Not resistant to:*Acetic acid concentrated*Acetic acid 10%*HCl 2%*HCl 36%*HF 40%*H2O2 30%*HNO3 2%*H3PO4 10%*H3PO4 concentrated*H2SO4 2%*H2SO4 98%
===PC (Polycarbonate)===
===PETT===According to [httphttps://taulman3dwww.curbellplastics.com/tResearch-glaseSolutions/Technical-features.html Taulman TResources/Technical-glaseResources/Chemical-Resistance-Chart Curbell plastics] is made of PETT., resistant to following chemicals:===FEP===*Acetic acid 5%Should be in the sweet spot of fluoropolymers. Low enough melting point *Acetic acid 10%*HCl 2%*HCl 36%*HNO3 2%*H3PO4 10%*H3PO4 concentrated*H2SO4 2%*H2O cold*H2O2 30% (according to be printable but chemically very durable[http://www. According to some data should be resistant to nearly all room temperature liquid chemiclas used in clean roomsensinger-online.com/fileadmin/pictures-pdf/Download/Brochures/ENS-Stock_shapes_Chem-Resistance_14.pdf Ensinger table])
===PEI===Limited resistance to:Ultem(R) is a commercial plastic which mainly consists of PEI.*Ethanol 96%===Nylon===[http://taulman3d.com/alloy-910-spec.html Taulman Alloy 910] is [https://www.youtube.com/watch?v=8_pt_05BqYk apparently] Nylon-based.*HF 40%===PETG===*IPAPolyethylene terephthalate modified with glycol.*H2O warm
Not resistant to:
*Acetic acid concentrated
*Acetone
*Ammonia solution 10%
*H2SO4 98%
===PEI (Polyetherimide)===
Ultem(R) is a commercial name for a family of PEI products.
==Organic polymers== General level discussion of organic polymers According to [https://www.Focus here in differences of organic polymerscurbellplastics.com/Research-Solutions/Technical-Resources/Technical-Resources/Chemical-Resistance-Chart Curbell plastics] and [http://www.ensinger-online.com/fileadmin/pictures-pdf/Download/Brochures/ENS-Stock_shapes_Chem-Resistance_14.pdf Ensinger], their production, etc Ultem(R) is resistant to following chemicals:*Acetic acid 5%*Acetic acid 10%*Ethanol 96%*HCl 2%*HCl 36%*IPA*HNO3 2%*H3PO4 10%*H2SO4 2%*H2O cold
==Fluoro polymers== Contrast these guys Limited resistance to organics:*H2O2 30%
===Sources===Journal Articles*Mark D. Symes, Philip J. Kitson, Jun Yan, Craig J. Richmond, Geoffrey J. T. Cooper, Richard W. Bowman, Turlif Vilbrandt & Leroy CroninNot resistant to: [https://www.nature.com/articles/nchem.1313 Integrated 3D-printed reactionware for chemical synthesis and analysis], Nature Chemistry 4, 349–354 (2012), doi:10.1038/nchem.1313*Philip J. Kitson, Mali H. Rosnes, Victor Sans, Vincenza Dragone and Leroy Cronin: [http://pubs.rsc.org/en/Content/ArticleLanding/2012/LC/c2lc40761b#!divAbstract Configurable 3D-Printed millifluidic and microfluidic ‘lab on a chip’ reactionware devices], Lab Chip, 2012, 12, 3267–3271. DOI: 10.1039/c2lc40761bAcetic acid concentrated*Jennifer S. Mathieson, Mali H. Rosnes, Victor Sans, Philip J. Kitson and Leroy Cronin: [https://www.beilstein-journals.org/bjnano/articles/4/31 Continuous parallel ESI-MS analysis of reactions carried out in a bespoke 3D printed device], Beilstein J. Nanotechnol. 2013, 4, 285–291. doi:10.3762/bjnano.4.31Acetone*Philip J. Kitson , Mark D. Symes , Vincenza Dragone and Leroy Cronin: [http://pubs.rsc.org/en/content/articlehtml/2013/sc/c3sc51253c Combining 3D printing and liquid handling to produce user-friendly reactionware for chemical synthesis and purification], Chem. Sci., 2013, 4, 3099-3103. DOI: Ammonia solution 10.1039/C3SC51253C%*Bethany C. Gross, Jayda L. Erkal, Sarah Y. Lockwood, Chengpeng Chen, and Dana M. Spence: [http://pubs.acs.org/doi/abs/10.1021/ac403397r Evaluation of 3D Printing and Its Potential Impact on Biotechnology and the Chemical Sciences], Anal. Chem., 2014, 86 (7), pp 3240–3253, DOI: 10.1021/ac403397r*Philip J. Kitson, Stefan Glatzel, Wei Chen, Chang-Gen Lin, Yu-Fei Song,and Leroy Cronin: [https://www.nature.com/articles/nprot.2016.041.pdf 3D printing of versatile reactionware for chemical synthesis], Nat. Protocols, 2016, 11 (5), 920-936HF 40%*H2SO4 98%
Other:
*Conflicting information in the charts for H2O warm
*No data available for H3PO4 concentrated
Chemical resistance charts===PETG (Polyethylene terephthalate modified with glycol)===*PET is used in plastic bottles and food packaging, while [https://www.curbellplasticsall3dp.com/Research-Solutions1/Technicalpetg-Resources/Technicalfilament-Resources3d-printing/Chemical-Resistance-Chart Curbell PlasticsPETG]*[http://sevierlab(Polyethylene terephthalate modified with glycol) is used in 3D printing.vet.cornell.edu/resources/Chemical-Resistance-Chart-Detail.pdf Thermo Scientific Nalgene Products]Glass transition temperature 88°C, Cornell University Sevier lab*[http://wwwless brittle than PET.ensinger-online.com/fileadmin/pictures-pdf/Download/Brochures/ENS-Stock_shapes_Chem-Resistance_14.pdf Ensinger Plastics]*[http://www.sirmax.it/sites/default/files/Chemical%20resistance%20of%20polymers.pdf Sirmax]
Books===PETT (Polyethylene coTrimethylene Terephthalate)===*SchreirsAnother variant to PET, Jtransparent. [httpshttp://bookstaulman3d.googlecom/t-glase-features.fihtml Taulman T-glase] is made of [https:/books?hl/all3dp.com/1/petg-filament-3d-printing/ PETT]. =fi&lr=&id=08y8kcvRS6AC&oiPLA (Polylactic acid)=fnd&pg=PA3&dq=fluoropolymer+chemical+resistance&otsOne of the most used 3D printing filaments. Various vendors and available in multiple colors. Biodegradable, potentially not very resistant to chemicals. =S-_sDXzXtG&sig=NDvFlfAP4WyGG9tPN5C6bSzYqUU&redir_esc=y#vPP (Polypropylene)=onepage&q=fluoropolymer%20chemical%20resistance&f=false Modern fluoropolymersResistant to various laboratory chemicals.] Scheirs, JQuite resistant to acids and bases., Ed (1997): 32Widely used in clean rooms.*MoiseevIs susceptible to oxidation for example peroxides, Yu Vas it is just a hydrocarbon., and Gennadiĭ Efremovich Zaikov3D printed polypropylene demonstrated in various chemical applications by Kitson et al.  According to [https://bookswww.googlecurbellplastics.ficom/books?hl=en&lr=&id=8N2Research-fzAFw18C&oi=fnd&pg=PA1&ots=lIjOuftT7lsig=YtNNWguSLSGCe48AjzOpid_u_i0&redir_esc=y#v=onepage&q&f=false Solutions/Technical-Resources/Technical-Resources/Chemical resistance of polymers in aggressive media-Resistance-Chart Curbell plastics]. Springer Science & Business Media, 1987.resistant to following chemicals:*Seymour RAcetic acid 5%*Acetic acid 10%*Acetic acid concentrated*Acetone*Ammonia solution 10%*Ethanol 96%*HCl 2%*HCl 36%*HF 40%*H2O2 30%*IPA*HNO3 2%*H3PO4 10% (according to [http://www.Bensinger-online., Carraher C.Ecom/fileadmin/pictures-pdf/Download/Brochures/ENS-Stock_shapes_Chem-Resistance_14. pdf Ensinger table]*H3PO4 concentrated*H2SO4 2%*H2SO4 98%*H2O cold*H2O warm Limited resistance to:*Acetic acid concentrated (1984) according to [httpshttp://linkwww.springerensinger-online.com/chapterfileadmin/10pictures-pdf/Download/Brochures/ENS-Stock_shapes_Chem-Resistance_14.1007pdf Ensinger table]*H2O warm (according to [http:/978/www.ensinger-1online.com/fileadmin/pictures-4684pdf/Download/Brochures/ENS-4748Stock_shapes_Chem-4_10 Chemical Resistance of PolymersResistance_14.pdf Ensinger table]. In Not resistant to: Structure—Property Relationships in Polymers. Springer, Boston, MA.-
===Searches===
Google:
*Chemical resistance of 3D printing materials
*Fused filament fabrication materials resistance
*Chemical resistance of polymers
 
 
 
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