3D Printing of Micropatterned Anion Exchange Membranes

Jiho Seo, Douglas I. Kushner, Michael Anthony Hickner

Research output: Contribution to journalArticle

24 Citations (Scopus)

Abstract

Micropatterned anion exchange membranes (AEMs) have been 3D printed via a photoinitiated free radical polymerization and quaternization process. The photocurable formulation, consisting of diurethane dimethacrylate (DUDA), poly(ethylene glycol) diacrylate (PEGDA), dipentaerythritol penta-/hexa- acrylate, and 4-vinylbenzyl chloride (VBC), was directly cured into patterned films using a custom 3D photolithographic printing process similar to stereolithography. Measurements of water uptake, permselectivity, and ionic resistance were conducted on the quaternized poly(DUDA-co-PEGDA-co-VBC) sample series to determine their suitability as ion exchange membranes. The water uptake of the polymers increased as the ion exchange capacity (IEC) increased due to greater quaternized VBC content. Samples with IEC values between 0.98 to 1.63 mequiv/g were synthesized by varying the VBC content from 15 to 25 wt %. The water uptake was sensitive to the PEGDA content in the network resulting in water uptake values ranging from 85 to 410 wt % by varying the PEGDA fractions from 0 to 60 wt %. The permselectivity of the AEM samples decreased from 0.91 (168 wt %, 1.63 mequiv/g) to 0.85 (410 wt %, 1.63 mequiv/g) with increasing water uptake and to 0.88 (162 wt %, 0.98 mequiv/g) with decreasing IEC. Permselectivity results were relatively consistent with the general understanding of the correlation between permselectivity, water uptake, and ion content of the membrane. Lastly, it was revealed that the ionic resistance of patterned membranes was lower than that of flat membranes with the same material volume or equivalent thickness. A parallel resistance model was used to explain the influence of patterning on the overall measured ionic resistance. This model may provide a way to maximize ion exchange membrane performance by optimizing surface patterns without chemical modification to the membrane.

Original languageEnglish (US)
Pages (from-to)16656-16663
Number of pages8
JournalACS Applied Materials and Interfaces
Volume8
Issue number26
DOIs
StatePublished - Jul 6 2016

Fingerprint

Anions
Printing
Ion exchange
Negative ions
Membranes
Polyethylene glycols
Water
Chlorides
Ion exchange membranes
Stereolithography
Chemical modification
Free radical polymerization
Polymers
Ions
poly(ethylene glycol)diacrylate
diurethane dimethacrylate

All Science Journal Classification (ASJC) codes

  • Materials Science(all)

Cite this

Seo, Jiho ; Kushner, Douglas I. ; Hickner, Michael Anthony. / 3D Printing of Micropatterned Anion Exchange Membranes. In: ACS Applied Materials and Interfaces. 2016 ; Vol. 8, No. 26. pp. 16656-16663.
@article{abed7dd860bb4238be1292daae20bf27,
title = "3D Printing of Micropatterned Anion Exchange Membranes",
abstract = "Micropatterned anion exchange membranes (AEMs) have been 3D printed via a photoinitiated free radical polymerization and quaternization process. The photocurable formulation, consisting of diurethane dimethacrylate (DUDA), poly(ethylene glycol) diacrylate (PEGDA), dipentaerythritol penta-/hexa- acrylate, and 4-vinylbenzyl chloride (VBC), was directly cured into patterned films using a custom 3D photolithographic printing process similar to stereolithography. Measurements of water uptake, permselectivity, and ionic resistance were conducted on the quaternized poly(DUDA-co-PEGDA-co-VBC) sample series to determine their suitability as ion exchange membranes. The water uptake of the polymers increased as the ion exchange capacity (IEC) increased due to greater quaternized VBC content. Samples with IEC values between 0.98 to 1.63 mequiv/g were synthesized by varying the VBC content from 15 to 25 wt {\%}. The water uptake was sensitive to the PEGDA content in the network resulting in water uptake values ranging from 85 to 410 wt {\%} by varying the PEGDA fractions from 0 to 60 wt {\%}. The permselectivity of the AEM samples decreased from 0.91 (168 wt {\%}, 1.63 mequiv/g) to 0.85 (410 wt {\%}, 1.63 mequiv/g) with increasing water uptake and to 0.88 (162 wt {\%}, 0.98 mequiv/g) with decreasing IEC. Permselectivity results were relatively consistent with the general understanding of the correlation between permselectivity, water uptake, and ion content of the membrane. Lastly, it was revealed that the ionic resistance of patterned membranes was lower than that of flat membranes with the same material volume or equivalent thickness. A parallel resistance model was used to explain the influence of patterning on the overall measured ionic resistance. This model may provide a way to maximize ion exchange membrane performance by optimizing surface patterns without chemical modification to the membrane.",
author = "Jiho Seo and Kushner, {Douglas I.} and Hickner, {Michael Anthony}",
year = "2016",
month = "7",
day = "6",
doi = "10.1021/acsami.6b03455",
language = "English (US)",
volume = "8",
pages = "16656--16663",
journal = "ACS applied materials & interfaces",
issn = "1944-8244",
publisher = "American Chemical Society",
number = "26",

}

3D Printing of Micropatterned Anion Exchange Membranes. / Seo, Jiho; Kushner, Douglas I.; Hickner, Michael Anthony.

In: ACS Applied Materials and Interfaces, Vol. 8, No. 26, 06.07.2016, p. 16656-16663.

Research output: Contribution to journalArticle

TY - JOUR

T1 - 3D Printing of Micropatterned Anion Exchange Membranes

AU - Seo, Jiho

AU - Kushner, Douglas I.

AU - Hickner, Michael Anthony

PY - 2016/7/6

Y1 - 2016/7/6

N2 - Micropatterned anion exchange membranes (AEMs) have been 3D printed via a photoinitiated free radical polymerization and quaternization process. The photocurable formulation, consisting of diurethane dimethacrylate (DUDA), poly(ethylene glycol) diacrylate (PEGDA), dipentaerythritol penta-/hexa- acrylate, and 4-vinylbenzyl chloride (VBC), was directly cured into patterned films using a custom 3D photolithographic printing process similar to stereolithography. Measurements of water uptake, permselectivity, and ionic resistance were conducted on the quaternized poly(DUDA-co-PEGDA-co-VBC) sample series to determine their suitability as ion exchange membranes. The water uptake of the polymers increased as the ion exchange capacity (IEC) increased due to greater quaternized VBC content. Samples with IEC values between 0.98 to 1.63 mequiv/g were synthesized by varying the VBC content from 15 to 25 wt %. The water uptake was sensitive to the PEGDA content in the network resulting in water uptake values ranging from 85 to 410 wt % by varying the PEGDA fractions from 0 to 60 wt %. The permselectivity of the AEM samples decreased from 0.91 (168 wt %, 1.63 mequiv/g) to 0.85 (410 wt %, 1.63 mequiv/g) with increasing water uptake and to 0.88 (162 wt %, 0.98 mequiv/g) with decreasing IEC. Permselectivity results were relatively consistent with the general understanding of the correlation between permselectivity, water uptake, and ion content of the membrane. Lastly, it was revealed that the ionic resistance of patterned membranes was lower than that of flat membranes with the same material volume or equivalent thickness. A parallel resistance model was used to explain the influence of patterning on the overall measured ionic resistance. This model may provide a way to maximize ion exchange membrane performance by optimizing surface patterns without chemical modification to the membrane.

AB - Micropatterned anion exchange membranes (AEMs) have been 3D printed via a photoinitiated free radical polymerization and quaternization process. The photocurable formulation, consisting of diurethane dimethacrylate (DUDA), poly(ethylene glycol) diacrylate (PEGDA), dipentaerythritol penta-/hexa- acrylate, and 4-vinylbenzyl chloride (VBC), was directly cured into patterned films using a custom 3D photolithographic printing process similar to stereolithography. Measurements of water uptake, permselectivity, and ionic resistance were conducted on the quaternized poly(DUDA-co-PEGDA-co-VBC) sample series to determine their suitability as ion exchange membranes. The water uptake of the polymers increased as the ion exchange capacity (IEC) increased due to greater quaternized VBC content. Samples with IEC values between 0.98 to 1.63 mequiv/g were synthesized by varying the VBC content from 15 to 25 wt %. The water uptake was sensitive to the PEGDA content in the network resulting in water uptake values ranging from 85 to 410 wt % by varying the PEGDA fractions from 0 to 60 wt %. The permselectivity of the AEM samples decreased from 0.91 (168 wt %, 1.63 mequiv/g) to 0.85 (410 wt %, 1.63 mequiv/g) with increasing water uptake and to 0.88 (162 wt %, 0.98 mequiv/g) with decreasing IEC. Permselectivity results were relatively consistent with the general understanding of the correlation between permselectivity, water uptake, and ion content of the membrane. Lastly, it was revealed that the ionic resistance of patterned membranes was lower than that of flat membranes with the same material volume or equivalent thickness. A parallel resistance model was used to explain the influence of patterning on the overall measured ionic resistance. This model may provide a way to maximize ion exchange membrane performance by optimizing surface patterns without chemical modification to the membrane.

UR - http://www.scopus.com/inward/record.url?scp=84977606110&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84977606110&partnerID=8YFLogxK

U2 - 10.1021/acsami.6b03455

DO - 10.1021/acsami.6b03455

M3 - Article

AN - SCOPUS:84977606110

VL - 8

SP - 16656

EP - 16663

JO - ACS applied materials & interfaces

JF - ACS applied materials & interfaces

SN - 1944-8244

IS - 26

ER -