Nicole M. Stark

Grafting of Bacterial Polyhydroxybutyrate (PHB) onto Cellulose via In Situ Reactive Extrusion with Dicumyl Peroxide

Polyhydroxybutyrate (PHB) was grafted onto cellulose fiber by dicumyl peroxide (DCP) radical initiation via in situ reactive extrusion. The yield of the grafted (cellulose-g-PHB) copolymer was recorded and grafting efficiency was found to be dependent on the reaction time and DCP concentration. The grafting mechanism was investigated by electron spin resonance (ESR) analysis and showed the presence of radicals produced by DCP radical initiation. The grafted copolymer structure was determined by nuclear magnetic resonance (NMR) spectroscopy. Scanning electronic microscopy (SEM) showed that the cellulose-g-PHB copolymer formed a continuous phase between the surfaces of cellulose and PHB as compared to cellulose-PHB blends. The relative crystallinity of cellulose and PHB were quantified from Fourier transform infrared (FTIR) spectra and X-ray diffraction (XRD) results, while the absolute degree of crystallinity was evaluated by differential scanning calorimetry (DSC). The reduction of crystallinity indicated the grafting reaction occurred not just in the amorphous region but also slightly in crystalline regions of both cellulose and PHB. The smaller crystal sizes suggested the brittleness of PHB was decreased. Thermogravimetric analysis (TGA) showed that the grafted copolymer was stabilized relative to PHB. By varying the reaction parameters the compositions (%PHB and %cellulose) of resultant cellulose-g-PHB copolymer are expected to be manipulated to obtain tunable properties.

Interfacial improvements in biocomposites based on poly(3-hydroxybutyrate) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) bioplastics reinforced and grafted with α-cellulose fibers

In this study, α-cellulose fibers reinforced green biocomposites based on polyhydroxybutyrate (PHB) and the copolymer poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) were prepared and characterized. The α-cellulose fibers were isolated from at-risk intermountain lodgepole pine wood by successive removal of extractives, lignin and hemicellulose. Grafting of PHB or PHBV onto cellulose was conducted using reactive extrusion with dicumyl peroxide free radical initiation at high temperature. It is postulated that the grafted copolymers at the interfaces of cellulose and the polymer matrix performed as an interfacial coupling agent. Grafting tended to interact with both the hydrophilic fibers and the hydrophobic PHB or PHBV matrix. The biocomposites were characterized by scanning electron microscopy (SEM) and dynamic mechanical analysis (DMA) and indicated good interfacial bonding and compatibility between the two phases. The mechanical properties of the biocomposites were improved by grafting due to improved stress transfer between the two interphases of the fiber/polymer matrix as compared to the blend control composite. The crystallinity of PHB, PHBV and cellulose in the biocomposite were reduced as determined by Fourier transform infrared spectroscopy (FTIR), wide-angle X-ray diffraction (WAXD), and differential scanning calorimetry (DSC) analyses. This in situ reactive extrusion process offers an effective approach to improve the properties of biocomposite materials from sustainable resources.

Weathering Characteristics of Wood Plastic Composites Reinforced with Extracted or Delignified Wood Flour

This study investigated weathering performance of an HDPE wood plastic composite reinforced with extracted or delignified wood flour (WF). The wood flour was pre-extracted with three different solvents, toluene/ethanol (TE), acetone/water (AW), and hot water (HW), or sodium chlorite/acetic acid. The spectral properties of the composites before and after artificial weathering under accelerated conditions were characterized by Fourier transform infrared (FTIR) spectroscopy, the surface color parameters were analyzed using colorimetry, and the mechanical properties were determined by a flexural test. Weathering of WPC resulted in a surface lightening and a decrease in wood index (wood/HDPE) and flexural strength. WPCs that were reinforced with delignified wood flour showed higher ΔL* and ΔE* values, together with lower MOE and MOR retention ratios upon weathering when compared to those with non-extracted control and extracted WF.

Opportunities for cellulose nanomaterials in packaging films: a review and future trends

Performance requirements for packaging films may include barrier properties, transparency, flexibility, and tensile strength. Conventional packaging materials such as plastic films and laminates, are typically made from petroleum-based polymers. Currently, there is a drive to develop sustainable packaging materials. These alternative materials must be able to be manufactured economically and on a commercial scale, exhibit barrier properties and transparency, and provide adequate mechanical performance. As a biobased, renewable material, cellulose nanomaterials (CNs) are ideally suited to be used in sustainable packaging applications. CNs include cellulose nanocrystals (CNCs) and cellulose nanofibrils (CNFs) and each can provide benefit to packaging films. Manufactured CNF films can be used as packaging films or laminates and have been shown to have good strength properties and good barrier properties, particularly at low humidity. Both CNCs and CNFs can be added to other polymers to improve strength and barrier properties. The flexibility of CNs to be used in a variety of ways in packaging applications has resulted in considerable attention and research activity. This article summarizes the current applicability for CNs in packaging films and discusses the future trends and opportunities for these materials.

Use of saltcedar and Utah juniper as fillers in wood-plastic composites.

Invasive and small-diameter species have become more prevalent, creating numerous environmental and ecological problems. One potential method to control and eliminate invasive species and thereby promote natural rangeland restoration is developing new, value-added uses for them. Saltcedar (Tamarisk ramosissima) and Utah juniper (Juniperus osteosperma) were investigated for use as fillers in wood–plastic composites (WPCs). The chemical composition and thermal stability of wood flours from both invasive species were compared with those of commercial pine wood flour. The wood flours were compounded with plastic and additives, and the viscosities of the composite melts containing the different species were compared. Composites produced from the compounded material by profile extrusion and injection molding were evaluated for mechanical performance, appearance, and weatherability. Saltcedar wood flour had the most minerals and water soluble extractives, which resulted in the lowest thermal stability and the lowest melt viscosity when compounded with high-density polyethylene. Injection-molded WPCs made from saltcedar or juniper were both considerably darker than those made with pine but performed similarly in accelerated weathering tests. Their mechanical properties were generally lower than those of the composites made from pine, but appropriate application selection and proper design could help compensate. Extruded WPCs were successfully made with each of the species. Producing WPCs from these composites appears technically feasible, although continued formulation development and durability evaluation are needed so that informed decisions regarding applications can be made. Economically feasible applications that use the advantageous properties of these species and that can tolerate or address the less desirable ones need to be identified and demonstrated.

Preparation and characterization of the nanocomposites from chemically modified nanocellulose and poly(lactic acid)

Cellulose nanocrystals (CNCs) are renewable and sustainable filler for polymeric nanocomposites. However, their high hydrophilicity limits their use with hydrophobic polymer for composite materials. In this study, freeze-dried CNCs were modified by transesterification with canola oil fatty acid methyl ester to reduce the hydrophilicity. The transesterified CNCs (CNCFE) were compounded with PLA into nanocomposites. CNCFE with long-chain hydrocarbons plays a role as plasticizer. Increasing CNCFE loadings resulted in clear plasticizing effects. Lower Tg and Tm were achieved for CNCFE-based nanocomposites. Plasticizing nanocomposite melt with CNCFE can mitigate the degradation of CNCs during thermal processing. The elongation at break of nanocomposites containing 5% CNCFE was increased. Dynamic rheological study showed the highest elastic and viscous moduli (G′ and G′′) and complex viscosity (G*) of nanocomposites with addition of 2% CNCFE. By tailoring the loadings of the transesterified CNCs, tunable structure and properties of nanocomposites can be obtained.

Spectroscopic analysis of the role of extractives on heat-induced discoloration of black locust (Robinia pseudoacacia)

Abstract To investigate the role of extractives on heat-induced discoloration of wood, samples of black locust (Robinia pseudoacacia) wood flour were extracted with various solvents prior to heat-treatment. Analysis of their color parameters and chromophoric structures showed that the chroma value of the unextracted sample decreased while that of the extracted sample increased after heat-treatment. Both samples showed broad diffuse reflectance UV-Vis (DRUV) absorption bands with maxima around 360–380 nm after heat-treatment due to the formation of conjugated double bonds, carbonyl functionalities, and quinoid structures. Compared with the unextracted sample, the dominant chromaticity of the extracted samples hypochromatically shifted and the peak became narrower. This result showed that extractives contribute mostly to the reduction in the light reflection on heat-treated wood. In addition to extractives, lignin and hemicellulose also contributed to the formation of color substances upon heat-treatment. The increase in C3/C2 ratio in X-ray photoelectron spectroscopy (XPS) spectra signified the oxidation reactions in the heating process. The increase in O1/O2 for extracted sample after heat-treatment and changes in DRUV and Fourier transform infrared spectroscopy (FTIR) spectra support the hypothesis that discoloration can also arise from the degradation of hemicellulose and the condensation reactions of lignin.

Properties of wood-plastic composites (WPCs) reinforced with extracted and delignified wood flour

Abstract The water sorption and mechanical properties of wood-plastic composites (WPCs) made of extracted and delignified wood flour (WF) has been investigated. WF was prepared by extraction with the solvent systems toluene/ethanol (TE), acetone/water (AW), and hot water (HW), and its delignification was conducted by means of sodium chlorite/acetic acid (AA) solution. A 24 full-factorial experimental design was employed to determine the effects of treatments and treatment combinations. WPCs were prepared with high-density polyethylene (HDPE) and treated WF was prepared by means of extrusion followed by injection molding, and the water absorption characteristics and mechanical properties of the products were evaluated. WPCs produced with extracted WF had lower water absorption rates and better mechanical properties than those made of untreated WF. WPCs containing delignified WF had higher water absorption rates and improved mechanical performance compared with those made of untreated WF.