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Faster Curing in BMI for 3D Printing Ink

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Submitted:

30 December 2023

Posted:

03 January 2024

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Abstract
Bismaleimide (BMI) is a high-performance thermosetting resin widely used in the aerospace, automotive, and mechanical and electronics industries due to its chemical and mechanical stability. It also has the capability of being used as an ink in polyjets used for 3D printing evident from thinner mellamide FTIR bands and faster curing rates as observed from TGA-DSC studies.
Keywords: 
Subject: Chemistry and Materials Science  -   Materials Science and Technology

1. INTRODUCTION

Bismaleimide (BMI) resins are a class of high-performance thermosetting polymers with several advantageous properties that make them perfect for usage in a wide range of industrial applications, particularly those requiring aerospace components. They are very resistant to a variety of solvents, acids, and water, and they exhibit outstanding mechanical properties, low shrinkage, chemical resistance, and fire resistance. BMI coating has also been applied to stop rusting. The addition of inorganic materials, like metal oxides, can change the properties of the polymer as an inorganic-organic composite. There are several uses for organic-inorganic composites in the domains of chemistry, biology, electronics, and optics. [1,2,3,4,5].
BMI has been blended with titania, Ferric chloride as well as Graphene sheet. Metallization and APPJ treatment of Bismaleimide have shown better performance as corrosion protection and EMI shielding [6]. BMI monomers are molecules with two maleimide functional groups terminating them; they frequently contain several aromatic moieties to improve their curing properties. Figure 1a shows the typical structure of these compounds) [7,9]. The crystalline and structural configuration of the composite system has been reported earlier [8,9,10,11,12].
Additive manufacturing, also known as fast prototyping or 3D printing, is widely used in the creation of optical components, lab-on-a-chip devices, titanium scaffolds for orthopaedic implants, sophisticated biomedical devices, and aerial vehicle wing constructions. A low-cost and straightforward method for producing unique, customised components for biomedical as well as other uses is to use techniques like digital light processing (DLP) and polymer jetting. Compounds like poly(lactic acid) (PLA), acrylonitrile butadiene styrene (ABS-T), polycarbonate (PC), polydimethylsiloxane (PDMS), polyethylene terephthalate glycol (PET-G), polyurethane filaments (TPU) and polyamide (PA) [13]. BMI which is also from the family of polyamides having commendable chemical and mechanical properties is a potential ink for polyjets. Inorganic fillers added to BMI enhance the cross-linking causing improved performance (Figure 1b) [14].
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Figure 1. Basic structure of BMI [9] (self-drawn) (b)cross-linking of BMI (CC BY 4.0.) [14].
Figure 1. Basic structure of BMI [9] (self-drawn) (b)cross-linking of BMI (CC BY 4.0.) [14].
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2. MATERIALS & METHODS

Homide 250 (Diamino diphenyl methane bismaleimide-diamino diphenyl methane copolymer) was used as the BMI details of which are given in ref [2,6,7,12]. The process consisted of BMI being dissolved in distilled water and stirred with PVA and stirred.

3. RESULTS & DISCUSSIONS

A faster curing rate (which has been quantified by a parameter α) is a determining factor for an efficient Polyjet ink [15]. A smaller maleimide double bond width is indicative of a faster curing rate (Figure 2a, b). A TGA-DSC plot of heat-treated BMI (Figure 2c) is shown in Figure 2d which shows weight loss and is indicative of the fact that after 370oC, crystalline nature is obtained [12]. The sample before and after the study is shown as an inset. A shoulder peak at 110oC and the peak at 370oC indicates two curing regimes. The first one attribute to Ene reaction between allyl (−CH₂−HC=CH₂) and maleimide group and is endothermic in nature, whereas the second peak is due to Diel-Alder reaction, thermal rearrangement, cross-linking and dehydration of hydroxyl [16]. The rate of weight loss increases ten times showing a faster curing rate as required for the 3D printing ink.

4. CONCLUSIONS

Pristine BMI showed maleimide bands of low width indicative of faster curing rates which got confirmed from TGA-DSC studies with two different curing regimes. A higher weight loss with respect to temperature and cross-linking proved BMI to be efficient ink for Polyjet 3D printing.

Funding

No funding was received for conducting the research

Institutional Review Board Statement

The manuscript has not been submitted in parallel either in full or partially to any other journal.

Data Availability Statement

Data shall be provided on request

Acknowledgements

The author hereby thanks Prof. S. Bhowmik for valuable suggestions

Conflicts of Interest

There is no conflict of interest among the authors.

References

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  3. HOS Technik. Production of high-temperature resins - polybenzimidazole, bismaleimide, catalysts. Available online: http://www.hos-tec.com.
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  6. Bhattacharyya AS, Kumar S, Sharma A, Kumar D, Patel SB, Paul D, Dutta PP, Bhattacharjee G, Metallization and APPJ treatment of Bismaleimide, arXiv preprint arXiv:1508.04933, 2015 [cond-mat.mtrl-sci].
  7. Bhattacharyya AS, Kumar S, Sharma A, Kumar D, Patel SB, Paul D, Dutta PP, Bhattacharjee G, Metallization and APPJ treatment of Bismaleimide, High Performance Polymer, 2017, 29 (7), 816-826. [CrossRef]
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  13. I. Gouzman, N. Atar, E. Grossman, R. Verker, A. Bolker, M. Pokrass, S. Sultan, O. Sinwani, A. Wagner, T. Lück, Ch. Seifarth, 3D Printing of Bismaleimides: From New Ink Formulation to Printed Thermosetting Polymer Objects. Adv. Mater. Technol. 2019, 4, 1900368. [CrossRef]
  14. Shaoyun Chen, Lanqin Yu, Shiyu Zhang, Xiaolu Sun, Bo Qu, Rui Wang, Yanyu Zheng, Xiaoying Liu, Wenjie Li, Jianhong Gao, Dongxian Zhuo,Synergistic strengthening and toughening of 3D printing photosensitive resin by bismaleimide and acrylic liquid-crystal resin, Journal of Science: Advanced Materials and Devices, 8(3), 2023, 100565. [CrossRef]
  15. Wagner, Annika, Gouzman, Irina, Atar, Nurit, Grossman, Eitan, Pokrass, Mariana, Fuchsbauer, Anita, Schranzhofer, Leo and Paulik, Christian. (2019), Cure kinetics of bismaleimides as basis for polyimide-like inks for PolyJet™-3D-printing. J. Appl. Polym. Sci., 136, 47244. [CrossRef]
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Figure 2. (a) FTIR of BMI cured at 100oC showing (b) maleimide bands of low widths (c) TGA-DSC under nitrogen atmosphere of heat-treated BMI [12] .
Figure 2. (a) FTIR of BMI cured at 100oC showing (b) maleimide bands of low widths (c) TGA-DSC under nitrogen atmosphere of heat-treated BMI [12] .
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