An official website of the United States government
ABSTRACT Brown grease (BG) is a high‐free fatty acid (FFA) waste coproduct from the food industry that remains largely unexploited. Herein, we describe a design strategy to upcycle BG into high sulfur‐content materials (HSMs) via inverse vulcanization, circumventing the need for costly transition metals or food‐grade compatibilizers. First, BG was esterified with methyl or allyl groups, yielding MeBG and aBG, respectively. This modification masked the polar carboxylic acids and enhanced miscibility with molten sulfur. Subsequent inverse vulcanization produced remeltable HSMs at 80 or 90 wt% sulfur with uniform elemental distributions by SEM–EDX. FT‐IR spectroscopy revealed the consumption of C=C moieties and the formation of C–S bonds, signifying robust cross‐linking. Thermal analysis (TGA, DSC) indicated good thermal stability (Td,5%up to 223°C) and glass transitions characteristic of polysulfide networks. Mechanical evaluations demonstrated compressive strengths up to 19.2 MPa, exceeding the minimum requirement for residential foundation‐grade cement (17 MPa) and rivaling previously reported HSMs containing similarly high sulfur content. Notably, MeBG and aBG incorporate organics comprising up to 97 wt% BG, significantly improving the upcycled mass efficiency relative to earlier BG‐based composites. This esterification‐driven approach thus offers a practical, scalable pathway to convert low‐value BG into advanced materials with tunable thermomechanical properties.
more »
« less
Composites produced from waste plastic with agricultural and energy sector by‐products
Abstract A three‐stage route to chemically upcycle post‐consumer poly(ethylene terephthalate) (PET) to produce high compressive strength composites is reported. This procedure involves initial glycolysis with diethylene glycol to produce a mixture (GPET) comprising oligomers of 2–7 terephthalate units followed by trans/esterification of GPET with fatty acid chains supplied by brown grease, an agricultural by‐product of animal fat of relatively low nutritional or fuel value. This process yields PGB comprising a mixture of mono‐terephthalate ester derivatives. The olefin units provided by unsaturated fatty acid chains in brown grease were crosslinked by an inverse vulcanization reaction with elemental sulfur to give composites GBSx(x = wt% S, varied from 80%–90%). The compressive strengths of GBS80(27.5 ± 2.6 MPa) and GBS90(19.2 ± 0.8 MPa) exceed the compressive strength required of ordinary Portland cement (17 MPa) for its use in residential building foundations. The current route represents a way to repurpose waste plastic, energy sector by‐product sulfur, and agricultural by‐product brown grease to give high strength composites with mechanical properties suggesting their possible use to replace less sustainably sourced legacy structural materials.
more »
« less
- Award ID(s):
- 2203669
- PAR ID:
- 10472834
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Journal of Applied Polymer Science
- Volume:
- 141
- Issue:
- 3
- ISSN:
- 0021-8995
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract Rancid animal fats unsuitable for human or animal food production represent low‐value and abundant, yet underexploited organic chemical precursors. The current work describes a strategy to synthesize high sulfur‐content materials (HSMs) that directly utilizes a blend of partially hydrolyzed chicken fat and plant oils as the organic comonomers, following up on analogous reactions using brown grease in place of chicken fat. The reaction of sulfur and chicken fat with either canola or sunflower oil yielded crosslinked polymer composites CFSxor GFSx, respectively (x = wt% sulfur, varied from 85%–90%). The composites exhibited compressive strengths of 24.7–31.7 MPa, and flexural strengths of 4.1–5.7 MPa, exceeding the value of established construction materials like ordinary Portland cement (compressive strength ≥17 MPa required for residential building, flexural strength 2–5 MPa). The composites also exhibited thermal stability up to 215–224 °C. The simple single‐step protocol described herein represents a way to upcycle an affordable and previously unexploited animal fat resource to form structural composites via the atom economical inverse vulcanization mechanism.more » « less
-
Abstract Herein high-strength composites are prepared from elemental sulfur, sunflower oil, and wastewater sludge. Fats extracted from dissolved air flotation (DAF) solids were reacted with elemental sulfur to yield compositeDAFS(10 wt% DAF fats and 90 wt% sulfur). Additional composites were prepared from DAF fat, sunflower oil and sulfur to giveSunDAFx(x = wt% sulfur, varied from 85–90%). The composites were characterized by spectroscopic, thermal, and mechanical methods. FT-IR spectra revealed a notable peak at 798 cm–1indicating a C–S stretch inDAFS,SunDAF90, andSunDAF85indicating successful crosslinking of polymeric sulfur with olefin units. SEM/EDX analysis revealed homogenous distribution of carbon, oxygen, and sulfur inSunDAF90andSunDAF85. The percent crystallinity exhibited byDAFS(37%),SunDAF90(39%), andSunDAF85(45%) was observed to be slightly lower than that of previous composites prepared from elemental sulfur and fats and oils.DAFSandSunDAFxdisplayed compressive strengths (26.4–38.7 MPa) of up to 227% above that required (17 MPa) of ordinary Portland cement for residential building foundations. The composite decomposition temperatures ranged from 211 to 219 °C, with glass transition temperatures of − 37 °C to − 39 °C. These composites thus provide a potential route to reclaim wastewater organics for use in value-added structural materials having mechanical properties competitive with those of commercial products.more » « less
-
Abstract Environmental damage caused by waste plastics and downstream chemical breakdown products is a modern crisis. Endocrine‐disrupting bisphenol A (BPA), found in breakdown products of poly(bisphenol A carbonate) (PC), is an especially pernicious example that interferes with the reproduction and development of a wide range of organisms, including humans. Herein we report a single‐stage thiocracking method to chemically upcycle polycarbonate using elemental sulfur, a waste product of fossil fuel refining. Importantly, this method disintegrates bisphenol A units into monoaryls, thus eliminating endocrine‐disrupting BPA from the material and from any potential downstream waste. Thiocracking of PC (10 wt%) with elemental sulfur (90 wt%) at 320 °C yields the highly crosslinked networkSPC90. The composition, thermal, morphological, and mechanical properties ofSPC90were characterized by FT‐IR spectroscopy, TGA, DSC, elemental analysis, SEM/EDX, compressive strength tests, and flexural strength tests. The compositeSPC90(compressive strength = 12.8 MPa, flexural strength = 4.33 MPa) showed mechanical strengths exceeding those of commercial bricks and competitive with those of mineral cements. The approach discussed herein represents a method to chemically upcycle polycarbonate while deconstructing BPA units, and valorizing waste sulfur to yield structurally viable building materials that could replace less‐green legacy materials.more » « less
-
Abstract Here are reported composites made by crosslinking unsaturated units in canola, sunflower, or linseed oil with sulfur to yieldCanS,SunS, andLinS, respectively. These plant oils were selected because the average number of crosslinkable unsaturated units per triglyceride vary from 1.3 for canola to 1.5 for sunflower and 1.8 for linseed oil. The remeltable composites show compressive strengths that increase with increasing unsaturation number fromCanS(9.3 MPa) toSunS(17.9 MPa) toLinS(22.9 MPa). These values forSunSandLinSare competitive when compared with the value of 17 MPa required for residential building using traditional Portland cement. The plant oil composites are recyclable over many cycles and can retain up to 100% of strength after 24 hr in oxidizing acid under conditions where Portland cement is dissolved in under 30 min. Infusion of the composites into premade cement blocks affords them with significantly improved acid resistance as well. This work thus provides a simple, nearly 100% atom economical route to convert plant oils and waste sulfur to composites having enhanced performance over commercial structural materials.more » « less
