Dongling Qiao

Preparation and characterization of slow-release fertilizer encapsulated by starch-based superabsorbent polymer.

To enhance the effectiveness of fertilizers, a novel double-coated slow-release fertilizer was developed using ethyl cellulose (EC) as inner coating and starch-based superabsorbent polymer (starch-SAP) as outer coating. For starch-SAPs synthesized by a twin-roll mixer using starches from three botanical origins, a reduced grid size and an increased fractal gel size on nano-scale (i.e., increased stretch of 3D network) contributed to increasing the water absorbing capacity with a reduced absorbing rate and thus improving the slow-release property of fertilizer. The fertilizer particles coated with starch-SAP displayed well slow-release behaviors. In soil, compared to urea particles without and with EC coating, the particles further coated with starch-SAP showed reduced nitrogen release rate, and in particular, those with potato starch-SAP coating exhibited a steady release behavior for a period longer than 96h. Therefore, this work has demonstrated the potential of this new slow-release fertilizer system for improving the effectiveness of fertilizers.

Structural features and thermal property of propionylated starches with different amylose/amylopectin ratio

This work concerned the effects of amylose/amylopectin ratio on the structure and thermal stability of propionylated starches with high degree of substitution (DS). Four starches with different amylose content were used to obtain propionylated starches. Acylation partly disrupted granule morphology of native starches, and the imperfection and porous structures of starch granule were intensified along with the increased amylose content. It was noted that the crystalline structure of starch was destroyed and thus intense acylation occurred in both amorphous and crystalline regions. The acylated starch with high-amylose content displayed more ordered region compared to low-amylose starch. Acylation enhanced the thermal stability of starch, and this effect became more evident as the amylose content increased. Thus, the amylose/amylopectin ratio has been confirmed capable of affecting the structure and thermal behaviors of hydrophobic propionylated starch, which is of value for the design of starchy materials with tailored thermal stability.

Insights into the hierarchical structure and digestion rate of alkali-modulated starches with different amylose contents

Combined analytical techniques were used to explore the effects of alkali treatment on the multi-scale structure and digestion behavior of starches with different amylose/amylopectin ratios. Alkali treatment disrupted the amorphous matrix, and partial lamellae and crystallites, which weakened starch molecular packing and eventually enhanced the susceptibility of starch to alkali. Stronger alkali treatment (0.5% w/w) made this effect more prominent and even transformed the dual-phase digestion of starch into a triple-phase pattern. Compared with high-amylose starch, regular maize starch, which possesses some unique structure characteristics typically as pores and crystallite weak points, showed evident changes of hierarchical structure and in digestion rate. Thus, alkali treatment has been demonstrated as a simple method to modulate starch hierarchical structure and thus to realize the rational development of starch-based food products with desired digestibility.

Hydration-induced crystalline transformation of starch polymer under ambient conditions

With synchrotron small/wide-angle X-ray scattering (SAXS/WAXS), we revealed that post-harvest hydration at ambient conditions can further alter the starch crystalline structure. The hydration process induced the alignment of starch helices into crystalline lamellae, irrespective of the starch type (A- or B-). In this process, non-crystalline helices were probably packed with water molecules to form new crystal units, thereby enhancing the overall concentration of starch crystallinity. In particular, a fraction of the monoclinic crystal units of the A-type starches encapsulated water molecules during hydration, leading to the outward movement of starch helices. Such movement resulted in the transformation of monoclinic units into hexagonal units, which was associated with the B-type crystallites. Hence, the hydration under ambient conditions could enhance the B-polymorphic features for both A-type and B-type starches. The new knowledge obtained here may guide the design of biopolymer-based liquid crystal materials with controlled lattice regularity and demanded features.

Preparation of Cassava Starch-based Superabsorbent Polymer Using a Twin-roll Mixer as Reactor *

Cassava starch-based superabsorbent polymer was successfully synthesized using a new technology that based on modification of a Haake twin-roll mixer as reactor. The cassava starch was first gelatinized then modified by grafting under external shear stress in the reactor. The torque and temperature curves as a function of time can reflect the variations in the reactor and also offer some information about the copolymerization reaction. The advantages of this system include starch modification can be carried out (1) with high starch concentration, (2) under controlled time and (3) smaller amount of sample (60 g) required. The technology provides useful guides for reactive extrusion. The starch grafted composites were characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR) and thermal gravimetric analysis (TGA). The TGA was also used for determining the percentage of grafting ratio. The results show that the cassava starch has been successfully grafted with acrylamide then crosslinked by N,N′-methylene-bisacrylamide using this reactor. The ultimate water absorbent capacity of the cassava-based superabsorbent polymer impacted by various pH values illustrated that the acid and basic solutions inhibit the ability of imbibing water. Additionally, gel properties of the cassava-based superabsorbent polymer were investigated. It can be concluded that the structure of cassava gel is stable, while the three dimensional network of cassava-based superabsorbent polymer is rigid but its structure could not resist external force effectively and everlastingly since G′ was decreased with increasing amplitude.

Understanding the microstructure and absorption rate of starch-based superabsorbent polymers prepared under high starch concentration

From a microstructural view, the focus of this work was on the water absorption rate of starch-based superabsorbent polymers (starch-SAPs) prepared under high starch concentration (0.27:1w/w starch:water). The effects of starch amylose/amylopectin ratio were disclosed. The increase in amylopectin reduced the amount (CPAM) of polyacrylamide (PAM) in starch-SAPs but increased the ratio of starch carbons grafted with PAM, which eventually decreased the average length (LPAM) of PAM chains. The shorter PAM chains could reduce starch-SAP chain flexibility, thus inducing larger mass fractal gels in swollen starch-SAPs. In general, the increases in CPAM and LPAM were preferable for a higher water absorbent capacity (WAC), whereas the denser fractal gels reduced WAC. Interestingly, all starch-SAPs had a dual-phase absorption process with the first stage showing a higher rate than the second phase (k1>k2). The shorter PAM chains caused increases in k1 and k2.

An improved approach for evaluating the semicrystalline lamellae of starch granules by synchrotron SAXS

A fitting method combined with a linear correlation function was developed as an improved approach for the SAXS analysis of the semicrystalline lamellae of starch granules. Using a power-law function with two Gaussian plus Lorentz functions, the SAXS pattern was resolved into sub-patterns of the net lamellar peak and the power-law scattering plus scattering background (PL+B). The ratio of the net lamellar peak area (Apeak) to the total scattering area (Atotal) was proposed equal to the proportion of the lamellae within the starch granule (PSL). Along with this fitting method, we obtained a better profile of linear correlation function, with the elimination of the interference of non-lamellar amorphous starch (i.e., amorphous growth rings). Then, we could accurately calculate the lamellar parameters, e.g., PSL, the thicknesses of semicrystalline (d), crystalline (dc) and amorphous (da) lamellae, and the volume fraction (φc) of crystalline lamellae within semicrystalline lamellae. Quantitative analysis revealed that PSL was positively correlated with the crystallinity (Xc) of starch. It was confirmed that the distribution of lamellar thickness was more important than the starch botanical origin in affecting the validity of the developed fitting method. We also proposed a criterion to test the validity of the proposed method. Specifically, the total SAXS pattern should be mostly tangent to the profile of PL+B at a high q tail (close to 0.2Å-1).

Effect of alkanol surface grafting on the hydrophobicity of starch-based films

The surface hydrophobicity of starch-based films could be regulated using a two-step surface modification method. Such modification was realized by grafting with alkanols of different chain lengths (hexanol, dodecanol and octadecanol) on the surface of starch-based films. The grafting of alkanol increased the mobility of glycerol as the plasticizer within the film surface. Also, this grafting increased the mass ratio of carbon to oxygen on the film surface but reduced the mass ratio of carbon to nitrogen. Under the same reaction conditions, there were fewer dodecyl chains grafted onto the film surface than hexyl or octadecyl chains. Furthermore, the results revealed that the surface hydrophobicity of starch-based films could be enhanced by simply increasing the alkyl chain length. Also, fewer alkyl chains tended to reduce the surface hydrophobicity of the films. These results are valuable for the rational design of starch-based materials with demanded hydrophobic properties.

Synthesis and Characteristics of Graft Copolymerization of Starch-G-PAM Using A Twin-Roll Mixer as Reactor for Cornstarch with Different Amylose/Amylopectin Ratios

Abstract Starch-based superabsorbent polymers (SAPs) were produced by graft copolymerization of starch-g-acrylamide using a twin-roll mixer as reactor. This work focused on the effect of starch microstructure (amylose/amylopectin contents) from the same source (corn starch) on the graft ratio (GR), graft efficiency (GE) and Add-on (AO), as well as water absorption capability (WAC) of the SAPs, which were investigated by FTIR, NMR, gravimetric and TGA. The torque variation represented all the processing in the reactor, including compress, gelatinization, graft reaction and crosslinking. Results showed that all the starches were successfully grafted with acrylamide then crosslinked by N.N′-methylene-bisacrylamide through this technology. Both AO and GR increased with increasing amylose content. But the GE decreased with increasing amylose content, which is different from the results in the solution reaction. The higher WAC of high amylose starch-based SAP corresponds with higher AO and GR, while the higher WAC of waxy-based SAP corresponds with higher GE.