Lucian Lucia | North Carolina State University (original) (raw)

Papers by Lucian Lucia

Advanced Composites and Hybrid Materials, Sep 28, 2023

Deleted Journal, Feb 27, 2024

A preliminary assessment of the capacity of pulverized crab shells to function as bio-sorbents fo... more A preliminary assessment of the capacity of pulverized crab shells to function as bio-sorbents for the removal of selected metals, zinc, cadmium, and chromium was analyzed according to a factorial experimental design. These metals were chosen because they have little precedent in past sorption studies and represent metals discharged into receiving waters by the electroplating industry. The design was done to assess parameters that have the highest impact on adsorption capacity and removal efficiency. Validation with other heavy metal ion removals was performed for comparison followed by a factorial 33 DOE using JMP®. It was found that for zinc, adsorbent amount, pH, time and the interaction of adsorbent amount*time and pH*adsorbent amount have the highest significance. For cadmium, only adsorbent amount is significant. Finally, chromium uptake was strongly dependent on adsorbent amount and pH. According to ionic radius theory, the favorability for adsorption is according to the following trend: chromium > cadmium > zinc; however, under our set of experimental conditions, the order was: cadmium > zinc > chromium because the presence of calcium carbonate exerts a major role in their sequestration.

Bioresources, Apr 20, 2020

Prehydrolysis kraft pulping is an effective approach to produce dissolving pulp, which can be use... more Prehydrolysis kraft pulping is an effective approach to produce dissolving pulp, which can be used for viscose application. The prehydrolysis process using hot liquid water could remove hemicellulose and loosen the compact cell wall, thus facilitating subsequent pulping and bleaching processes. In this study, the composite severity factor (CSF) was used to reveal the intensity of prehydrolysis treatment and its effect on the pulping and bleaching process by combining the temperature, time, and pH variables. Results showed that the optimum CSF was 6.61, which produced a pulp with α-cellulose of 92.3%, degree of polymerization (DP) of 1081, brightness of 85.1% ISO, and Kappa number of 0.61. In addition, the fiber quality, crystalline structure, and microstructure of pulps were characterized by FQA (fiber quality analysis), XRD (X-ray diffraction), and SEM (scanning electron microscopy).

RSC Advances, 2017

The authors regret that a funding body was not included in the Acknowledgements section of the or... more The authors regret that a funding body was not included in the Acknowledgements section of the original article. A revised version of the Acknowledgements section, in which funding from the China Scholarship Council is included below. The Royal Society of Chemistry apologises for these errors and any consequent inconvenience to authors and readers.

Environmental Science & Technology, Jan 25, 2022

This review explores biobased polymers for industrial applications, their end fate, and most impo... more This review explores biobased polymers for industrial applications, their end fate, and most importantly, origin and key aspects enabling soil biodegradation. The physicochemical properties of biobased synthetic and natural polymers and the primary factors governing degradation are explored. Current and future biobased systems and factors allowing for equivalent comparisons of degradation and possible sources for engineering improved biodegradation are reviewed. Factors impacting ultraviolet (UV) stability of biopolymers have been described including methods to enhance photoresistance and impact on biodegradation. It discusses end-fate of biopolymers in soil and impact of residues on soil health. A limited number of studies examine side effects (e.g., microbial toxicity) from soil biodegradation of composites and biopolymers. Currently available standards for biodegradation and composting have been described with limitations and scope for improvements. Finally, design considerations and implications for sustainable polymers used, under consideration, and to be considered within the context of a rational biodegradable strategy are elaborated.

Polymer Reviews, Jun 5, 2023

Trends in green chemistry, 2019

Green chemistry is a sustainable chemistry that applies to several areas of environmental and agr... more Green chemistry is a sustainable chemistry that applies to several areas of environmental and agricultural sciences, geological sciences, green engineering and technology. Development of eco-friendly sustainable substances, pollution prevention is the main concept of green chemistry.

$Research paper thumbnail of Probing the molecular weights of sweetgum and pine kraft lignin fractions$

Tappi Journal, Jul 1, 2021

The present investigation undertook a systematic investigation of the molecular weight (MW) of kr... more The present investigation undertook a systematic investigation of the molecular weight (MW) of kraft lignins throughout the pulping process to establish a correlation between MW and lignin recovery at different extents of the kraft pulping process. The evaluation of MW is crucial for lignin characterization and utilization, since it is known to influence the kinetics of lignin reactivity and its resultant physicochemical properties. Sweetgum and pine lignins precipitated from black liquor at different pHs (9.5 and 2.5) and different extents of kraft pulping (30–150 min) were the subject of this effort. Gel permeation chromatography (GPC) was used to deter- mine the number average molecular weight (Mn), mass average molecular weight (Mw), and polydispersity of the lignin samples. It was shown that the MW of lignins from both feedstocks follow gel degradation theory; that is, at the onset of the kraft pulping process low molecular weightlignins were obtained, and as pulping progressed, the molecular weight peaked and subsequently decreased. An important finding was that acetobromination was shown to be a more effective derivatization technique for carbohydrates containing lignins than acetylation, the technique typically used for derivatization of lignin.

Bioresources, Jul 13, 2017

Lignin is an amorphous polymer that limits the enzymatic conversion of polysaccharides to ferment... more Lignin is an amorphous polymer that limits the enzymatic conversion of polysaccharides to fermentable sugars. Thus, a pretreatment that can enhance the accessibility of carbohydrates is a key step of successful biofuel conversion schemes. In this study, corn stover was fractioned into stem, cob, and leaf because their lignin is different. To elucidate the lignin changes, autohydrolysis, diluted acid, and alkali pretreatments were applied on the samples, followed by the isolation of cellulolytic enzyme lignin preparations. Alkaline nitrobenzene oxidation, 13 C-Nuclear Magnetic Resonance (NMR), and 1 H-13 C heteronuclear single quantum coherence NMR were used to profile the lignin changes. The results indicated that corn stover lignin is a p-hydroxyphenyl-guaiacyl-syringyltype lignin that incorporates p-coumarate and ferulate esters. The β-arylether was the most abundant inter-unit linkage, followed by condensed linkages, e.g. pino-/syringaresinol, phenylcoumaran, and spirodienone. As for the non-pretreated samples, leaf lignin was more condensed than stem lignin and cob lignin. More lignin was removed by the alkali pretreatment due to more cleavage of β-aryl-ether linkages. As a comparison, more condensed linkages were generated by the acidic pretreatments. The decrease of the syringyl/guaiacyl ratio indicated that the residual lignin became more condensed and confirmed that guaiacyl and p-hydroxyphenyl units were more stable than syringyl units during the pretreatment.

Fuel Processing Technology, Dec 1, 2017

Thermal reactions of six monomeric aromatics (typical primary pyrolytic products of β-O-4 lignin ... more Thermal reactions of six monomeric aromatics (typical primary pyrolytic products of β-O-4 lignin dimers) were studied in a closed ampoule reactor (N 2 /400-600°C/120 s) to obtain the information on secondary pyrolysis pathway of products. The result showed that the secondary pyrolysis of monomeric aromatics mainly included two pathways: polymerization and side-chain-conversion, and the polymerization were more competitive under all the test conditions. The amount of-OCH 3 group was an essential factor on the reactivity of monomeric aromatics, and the introduction of-OCH 3 group enhanced the conversion of monomeric aromatics. In the presence of-CHO group on the p-position of aryl-OH, the removal of-CHO group was major side-chain-conversion reaction during the pyrolysis process. Adding the amount of-OCH 3 group was beneficial for promotion the breakage of aryl-CHO bond; instead, when the p-position of phenolic hydroxyl group was-COCH 3 group, the cleavage of aryl-COCH 3 bond was inhibited, where radical induced rearrangement of aryl-OCH 3 group into aryl-CH 3 group firstly happened and as the major side-chain-conversion reaction. Besides, new reactant intermediates, which were directly formed via side-chain-conversion of initial samples, could further decompose to other aromatic monomers, and influenced the products distribution and selectivity via a series of reactions.

Journal of Analytical and Applied Pyrolysis, Jul 1, 2016

A process for the production of high-value-added phenolics following hydrothermal depolymerizatio... more A process for the production of high-value-added phenolics following hydrothermal depolymerization of black liquor lignins after acidification without catalysis was successfully deployed and is described herein. A high yield of liquid products up to 33.3 mg/mL (based on raw black liquor) was recovered at 290 °C, 30 min, and pH 6; meanwhile, only 12.6 mg/mL solid residue was obtained. GC-MS analyses of the liquid products confirmed value-added aromatic monomers, among which the yields of phenol, guaiacol, and 2, 6-dimethoxy-phenol were high (∼ 60% of the identified compounds). FT-IR of the solid residues indicated that the black liquor lignin was depolymerized through cleavage of ether bonds and decarboxylation. The results suggest that black liquor may be a new resource for aromatic products.

Cellulose, May 14, 2020

Cellulose nanocrystals (CNCs) were surface-modified using immobilized lipase (Novozyme 435) to ca... more Cellulose nanocrystals (CNCs) were surface-modified using immobilized lipase (Novozyme 435) to catalyze the formation of laurate ester groups on the CNC surface and thus facilitate homogeneous dispersion within a poly(lactic acid) (PLA) matrix. Results of dynamic contact angle measurement revealed that the modified CNCs (CNC-LAA) presented greater hydrophobicity than their CNC controls. FT-IR, 13 C-NMR, XRD, and TGA were used to characterize the structure and stability of the CNCs before and after modification. PLA reinforced with the modified CNCs were prepared, and the effect on mechanical properties was studied. SEM micrographs suggested uniform dispersion of modified CNCs throughout the PLA matrix at a maximum 1 wt% loading, which was found to be the optimal loading level. The CNC-LAA were able to achieve a 0.4 maximum degree of substitution. DSC indicated enhanced crystallization of PLA chains due to the inclusion of CNC-LAA, indicating that the nanofillers behaved as nucleating agents and also revealed improved compatibility. Tensile strength tests showed slightly improved mechanical properties for breaking strength and elongation at breakage.

ACS Sustainable Chemistry & Engineering, Nov 14, 2017

Lignin is a superb renewable feedstock for deriving petroleum-analogous biochemicals and value-ad... more Lignin is a superb renewable feedstock for deriving petroleum-analogous biochemicals and value-added bioproducts. However, proper elucidation of its original biosynthetic structure and subsequent deconstruction is necessary to facilitate proper exploitation. Herein, its chemical substructure and linkages within an important global Page 1 of 27 ACS Paragon Plus Environment ACS Sustainable Chemistry & Engineering 2 feedstock, rice straw, were interrogated by spectroscopy. Pyrolysis was chosen to cleave it and obtain guaiacyl (G), syringyl (S), and hydroxyphenyl (H) monophenols distributions at various temperatures. A unique relationship between product substructures and lignin depolymerization was revealed. The overall scope of the depolymerization mechanism into monophenols by cleavage of β-O-4 and β-5 in phenylcoumaran subunits were explored experimentally and through bond dissociation energy (BDE) theory.

Bioresources, Jul 5, 2017

Hydrochar was used to produce activated carbon with high BET surface area and large pore volume v... more Hydrochar was used to produce activated carbon with high BET surface area and large pore volume via phosphoric acid activation. The hydrochar described here can be obtained from hydrothermal carbonization of corn cob residue (CCR). Porous structure of activated carbons was characterized by nitrogen adsorption and scanning electron microscopy (SEM). Results showed that the specific surface area and total pore volume of activated carbon were increased to 2192 m 2 /g and 1.269 cm 3 /g, respectively, under conditions of 400 °C, 1 h, and an impregnation ratio of 3, from 5.69 m 2 /g and 0.136 cm 3 /g of the starting material. The chemical properties of hydrochar and activated carbons were further characterized by Fourier transform infrared spectroscopy (FT-IR), which confirmed the chemical transformation. Furthermore, the localized graphitic nature of the porous carbon was shown by the X-ray diffraction pattern. Thus, the adsorption capacity was enhanced for activated carbon in comparison with commercial carbon. The process of activated carbon preparation provided a high value-added application of hydrochar.

Carbohydrate Polymers, Oct 1, 2016

Starch nanocrystals (SNC) are aptly described as the insoluble degradation byproducts of starch g... more Starch nanocrystals (SNC) are aptly described as the insoluble degradation byproducts of starch granules that purportedly display morphologies that are platelet-like, round, square, and oval-like. In this work, we reported the preparation of SNC with unprecedented tubular structures through sulfuric acid hydrolysis of normal maize starch, subsequent exposure to ammonia and relaxation at 4°C. High-resolution transmission electron microscopy observation clearly proved that the SNCs possess tubular nanostructures with polygonal cross-section. After further reviewing the transformations of SNC by acid hydrolysis, ammonia treatment, and curing time at 4 °C, a mechanism for T-SNC formation is suggested. It is conjectured that T-SNC gradually self-assembles by combination of smaller platelet-like/square nanocrystals likely loosely aggregated by starch molecular chains from residual amorphous regions. This work paves the way for the pursuit of new approaches for the preparation of starch-based nanomaterials possessing unique morphologies.

ACS Sustainable Chemistry & Engineering, Jun 14, 2018

Active films containing curcumin exhibit outstanding antioxidant and antibacterial properties. Be... more Active films containing curcumin exhibit outstanding antioxidant and antibacterial properties. Because of curcumin's poor solubility in water, cetyltrimethylammonium chloride (CTAC) brush-TEMPO-oxidized cellulose nanocrystal (TCN) colloidal systems were prepared to be used as a delivery excipient to modulate the hosting of curcumin. The curcuminloaded cellulose nanocrystals were incorporated in a tara gum/ PVA blend film to prepare antioxidant and antibacterial films. Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) measurements, transmission electron microscope (TEM), and solid-state 13 C NMR spectroscopy were performed to characterize the products. The results indicate the synthesis of TCN with a carboxyl content of 1.1878 mmol/g and 0.71 degree of substitution of CTAC based on carboxyl groups. There was 26.57% of the curcumin bound in the brush. The mechanical properties and barrier properties of the films were characterized. DPPH and ABTS + assays were used to measure the antioxidant properties. The activities against Gram-negative (E. coli) and Gram-positive (S. aureus) bacteria were also evaluated. The release of curcumin from the films into food simulants were also characterized to determine whether the antioxidants could provide intermediate protection from lipid oxidation. The results show that the mechanical and barrier properties of the films improved although water the vapor permeability slightly decreased. The film possessed desirable antioxidant and antibacterial properties. The release test revealed that curcumin was initially released rapidly into 50% ethanol solution and then released more slowly into the bulk. This suggests that the film could provide short-term protection from food oxidation. The films can be used for prolonging the shelf life of packed fat-rich foods.

Chemical Engineering Journal, May 1, 2019

Wood has emerged as a sustainable and promising precursor for carbon materials owing to its natur... more Wood has emerged as a sustainable and promising precursor for carbon materials owing to its natural abundance and superb properties. It is of significant importance to prepare carbon materials with different morphologies (carbon spheres, carbon nanowires, carbon membranes, and three-dimensional carbon nanomaterials) and porous structures (disordered and ordered structure) for various fields (adsorption, capacitor, catalyst, solar cells, and sensors). Here, we introduce the characteristics of carbon materials with different morphologies from various biomass sources (Cedar, Starch, Chitin, Straw, Bamboo, and Larch sawdust) and present a comprehensive review of the current research on the development of carbon materials with different morphologies (carbon spheres, carbon membrane, and carbon foams) from liquefied wood. We then introduce control methods (direct carbonization, hydrothermal carbonization, and liquefaction-carbonization) that have been explored to prepare carbon materials with ordered porous structures. Next, we highlight the liquefaction method for the degradation and activity transformation of wood. In particular, we focus on the fabrication, characteristics and applications of carbon materials with different morphologies and porous structures produced from liquefied wood by different control methods (ultrasonic spray pyrolysis, soft template, doping, foaming, and nano-ething). Finally, we present our perspectives on supercapacitors, which need further exploration in the future for urban traffic systems, military equipment, intelligent distributed grid systems, new energy vehicles, solar energy systems, and wind turbine systems.

Bioresources, Jul 23, 2020

To achieve a better understanding of the pyrolysis behavior of pre-oxidized β-ether-type lignin, ... more To achieve a better understanding of the pyrolysis behavior of pre-oxidized β-ether-type lignin, three Cα=O type dimers with different substituent groups on the aromatic ring were synthesized and analyzed by a simultaneous thermal analysis instrument (STA), in-situ Fourier transform infrared spectroscopy (in-situ FTIR), and pyrolysis-gas chromatography/ mass spectrometry (Py-GC/MS). The results showed that major primary pyrolysis reactions of Cα=O type models normally occurred at 200 to 400 °C, and connecting bridge structures of models were completely destroyed, causing the emission of abundant volatiles. Substituent groups of aromatic rings played direct roles in thermal stability of models, volatiles emission, product characteristics, and secondary reaction pathways of major primary products. Particularly, the aryl-OCH3 group clearly enhanced the reactivity of intramolecular linkages and was an important active functional group for secondary reactions. As major primary products and intermediates, guaiacol and 2-methoxy-benzaldehyde were formed via the cleavage of Cα-O and Cα-Cβ bonds and could also be converted into phenol, benzaldehyde, and 2-methylphenol via rearrangement of aryl-OCH3 into an aryl-CH3 group or-OCH3 group removal. Oxidization of benzylic alcohol to benzylic ketone not only simplified depolymerization pathways, but also resulted in better selectivity of phenolic monomers and a predictable product distribution.