Molecular weight and uniformity define the mechanical performance of lignin-based carbon fiber

Li, Qiang; Serem, Wilson K.; Dai, Wei; Yue, Yuan; Naik, Mandar T.; Xie, Shangxian; Karki, Pravat; Liu, Li; Sue, Hung‐Jue; Liang, Hong; Zhou, Fujie; Yuan, Joshua S.

doi:10.1039/c7ta01187c

Cited by 87 publications

(44 citation statements)

References 27 publications

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“…In particular, we chose to focus on molecular weight and inter‐unit linkage abundance as these properties have not yet been obtained directly from FTIR spectra by chemometrics and are closely associated with the potential to valorise lignins. For example, β‐ O ‐4 content can significantly affect the potential to generate monomeric aromatic compounds from lignins and molecular weight may play a role in determining whether lignins are suitable for use in materials applications, for example in carbon‐fibre production …”

Section: Resultsmentioning

confidence: 99%

“…For example, b-O-4 content can significantly affect the potential to generate monomeric aromatic compoundsf rom lignins [13,38,39] and molecularw eight may play a role in determining whether lignins are suitable for use in materials applications, for example in carbon-fibre production. [40] Thus, PLS regressionm odels were built and optimised using the PLS To olboxw ithin MATLAB. PLS regression determines a linear regression model for the relationship between dependent variables (ATR-FTIR) andp redictor variables (NMR spectroscopy, GPC), which can then subsequently be used for making predictions based on ATR-FTIR measurements on new samples.…”

Section: Resultsmentioning

confidence: 99%

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Linkage Abundance and Molecular Weight Characteristics of Technical Lignins by Attenuated Total Reflection‐FTIR Spectroscopy Combined with Multivariate Analysis

Lancefield

Constant

Peinder³

et al. 2019

ChemSusChem

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Lignin is an attractive material for the production of renewable chemicals, materials and energy. However, utilization is hampered by its highly complex and variable chemical structure, which requires an extensive suite of analytical instruments to characterize. Here, we demonstrate that straightforward attenuated total reflection (ATR)‐FTIR analysis combined with principle component analysis (PCA) and partial least squares (PLS) modelling can provide remarkable insight into the structure of technical lignins, giving quantitative results that are comparable to standard gel‐permeation chromatography (GPC) and 2D heteronuclear single quantum coherence (HSQC) NMR methods. First, a calibration set of 54 different technical (fractionated) lignin samples, covering kraft, soda and organosolv processes, were prepared and analyzed using traditional GPC and NMR methods, as well as by readily accessible ATR‐FTIR spectroscopy. PLS models correlating the ATR‐FTIR spectra of the broad set of lignins with GPC and NMR measurements were found to have excellent coefficients of determination ( R 2 Cal.>0.85) for molecular weight ( M n , M w ) and inter‐unit abundances (β‐ O ‐4, β‐5 and β‐β), with low relative errors (6.2–14 %) as estimated from cross‐validation results. PLS analysis of a second set of 28 samples containing exclusively (fractionated) kraft lignins showed further improved prediction ability, with relative errors of 3.8–13 %, and the resulting model could predict the structural characteristics of an independent validation set of lignins with good accuracy. The results highlight the potential utility of this methodology for streamlining and expediting the often complex and time consuming technical lignin characterization process.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Linkage Abundance and Molecular Weight Characteristics of Technical Lignins by Attenuated Total Reflection‐FTIR Spectroscopy Combined with Multivariate Analysis

Lancefield

Constant

Peinder³

et al. 2019

ChemSusChem

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“…The most challenging issue in upgrading lignin wastes lies in the inherent heterogeneity of lignin polymer because of its various functional groups, diverse interunitary linkages, different molecular weight, and polydispersity . This heterogeneity could result from lignin biosynthesis during secondary cell‐wall thickening and be further augmented by biomass processing such as chemical pulping and pretreatment . Lignin was biosynthesized from three possible monomers of p ‐coumaryl, coniferyl, and sinapyl alcohols, which contain multiple hydroxy and methoxy groups to generate various functional groups for lignin .…”

Section: Figurementioning

confidence: 99%

“…Lignin heterogeneity could be reduced by suitable fractionation methods . Fractionation could purify lignin and separate it into different fractions with specific chemical features suitable for making different bioproducts .…”

Section: Figurementioning

confidence: 99%

“…Recent studies have proven the concept of effective fractionation for improving carbon fiber performance. Several fractionation techniques have been used for black liquor and Kraft lignin, including: 1) physical fractionation by membrane ultrafiltration and dialysis tube according to lignin molecular weight; 2) biological fractionation by using an enzyme‐mediator system; 3) solvent fractionation by using organic solvents with different solubilities of lignin; and 4) pH precipitation . Nevertheless, physical and biological fractionations are costly, solvent fractionation generally involves several organic solvents and/or complicated procedures, and pH precipitation may introduce new metal ions as impurities and is also a complex process.…”

Section: Figurementioning

confidence: 99%

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Non‐Solvent Fractionation of Lignin Enhances Carbon Fiber Performance

Lin

et al. 2019

ChemSusChem

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Lignin is an abundantn atural polymer in plants next to cellulose, yet also am ajor industrial waste produced from both lignocellulosic biorefinery and the paper-making industry. [1] Annually,a pproximately 50 million tons of lignin waste are generated from pulping mills. [2] This lignin waste stream could be furthera dded up to 300 million tons if the billion-ton initiative for lignocellulosic biofuels is implemented. [3] Even though upgradingl ignin into value-added products has been extensively soughta fter for decades to enhance economic return for the paper-making industry,t he current commercial utilization of lignin is mainly to burn the black liquor for heat recovery. [2, 4] Converting lignin waste into high-value products thus represents one of the most challenging issues for both the papermaking industry and lignocellulosic biorefinery.The most challenging issue in upgrading lignin wastes lies in the inherent heterogeneity of lignin polymer because of its variousf unctional groups, diversei nterunitary linkages, different molecular weight, and polydispersity. [4c, 5] This heterogeneity could result from lignin biosynthesis during secondary cellwall thickening and be furtheraugmented by biomass process-Even though lignin carbon fiber has been soughta fter for several decades, the poor mechanicalp erformance remains to be am ajor barrier for commercial applications. The low mechanical performance is attributed to the heterogeneity of lignin polymer.R ecent advances in fractionation technologies showedt he great potential to reduce lignin heterogeneity,b ut current fractionationm ethods often depend on costly chemicals and materials such as enzymes, organic solvents, membranes, and dialysis tubes.H ere, an ew non-solvent strategy was developed to fractionate lignin by autohydrolysis. By using only water,l ignin was efficiently fractionated into watersoluble and -insoluble fractions. The latterf raction had increasedm olecular weight and uniformity and resulted in more b-O-4 interunitary linkages as analyzed by size-exclusion chromatography and 2D heteronuclear single quantumc oherence NMR spectroscopy,r espectively.I np articular, the water-insoluble fraction significantly enhanced the mechanical performances of the resultant carbon fibers. Mechanistic study by differential scanning calorimetry (DSC) revealed that the miscibility of lignin with guest polyacrylonitrile molecules was improved with the reduced lignin heterogeneity.C rystallite analysesb y XRD and Raman spectroscopy revealed that the crystallite size and content of the pre-graphitict urbostratic carbon structure were increased. The fundamentalu nderstanding revealed how lignin fractionation could modify lignin chemical features to enhancet he mechanical performance of resultant carbon fibers. The autohydrolysis fractionation thus represents a green, economic, and efficient methodology to process lignin waste andb oost lignin carbon fiber quality,w hich could open new horizons for lignin valorization.

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Super Strong and Tough Hydrogels Constructed via Network Uniformization of Macromolecular Chains

Xu,

Tan,

Dong

et al. 2024

Adv Funct Materials

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The characteristic of materials with special strength and toughness is distinguished by the uniform arrangement of their multi‐level structures, which is a key factor that significantly affects their mechanical behavior and overall performance. This work explores the challenges and potential solutions to enhance the mechanical properties of hydrogels through the construction of multi‐scale, multi‐layered ordered uniform structures. A novel approach termed macromolecular network uniformization (MNU) that utilizes rotation ice templates to freeze‐cast uniform polymer networks in hydrogels is proposed. By integrating this process with salt‐out densification, hydrogels with exceptional toughness exceeding 350 MJ m⁻3 in both x and y directions with super‐high tensile stress (20 MPa) and strain at break (3000%), are obtained. This research effectively addresses the inherent limitation of hydrogel materials, which are primarily composed of hydrophilic polymers, limiting their potential for functional diversity and enhanced performance. To overcome this, the expansion of the hydrogel matrix is demonstrated to include hydrophobic polymers such as polycaprolactone (PCL) and polyacrylonitrile (PAN), thanks to the high solubility of DMSO. The MNU technique effectively produces high‐performance hydrogels with enhanced mechanical properties, increasing substrate diversity and enabling the development of durable hydrogel materials for various applications.

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Molecular weight and uniformity define the mechanical performance of lignin-based carbon fiber

Abstract: Quality lignin-based carbon fiber with high mechanical performance has been made from enzyme–mediator and dialysis fractionated lignin. In particular, the elastic modulus of lignin-based carbon fiber showed good correlations with PDI.

Cited by 87 publications

References 27 publications

Linkage Abundance and Molecular Weight Characteristics of Technical Lignins by Attenuated Total Reflection‐FTIR Spectroscopy Combined with Multivariate Analysis

Linkage Abundance and Molecular Weight Characteristics of Technical Lignins by Attenuated Total Reflection‐FTIR Spectroscopy Combined with Multivariate Analysis

Non‐Solvent Fractionation of Lignin Enhances Carbon Fiber Performance

Super Strong and Tough Hydrogels Constructed via Network Uniformization of Macromolecular Chains

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