Innovative Food Science & Emerging Technologies 12 (2011) 586593

Title: The effect of ball milling treatment on structure and porosity of maize starch granule
Authors: Tian Yi Liu, Ying Ma, Shi Feng Yu, John Shi, Sophia Xue
1. Introduction:
- Starch is the main storage carbohydrate of plants, 80% of the world market for starch, application in food and
industry are affected by its structure, such as relative crystallinity, the ratio of amylose to amylopectin, surface
morphology of starch granule and the particle diameters of granules.
- Several physical technologies, such as high pressure, pulsed electric fields, ultrasound, microwave, gamma
irradiation and heat-moisture treatment, to achieve particular structure and technological properties, such as
solubility, viscosity properties in solution, swelling and pasting properties, and digestibility.
- Ball milling treatment, as a cost-lowering and environmental-friendly physically modified method, has been used
to decrease effectively relative crystallinity and increase solubility and digestibility of starch. Ratio of pore volume
to granule volume, plays an important role in such phenomena as sorption, thermal conductivity, water diffusivity
and also influences their mechanical and textural properties.
- The objective is to precisely understand the variation of crystalline structure, to demonstrate the development of
central cavity and to elucidate pore and surface characteristics of starch during ball milling treatment through Xray diffraction, Fourier transforms infrared, 13C CP/MAS NMR, scanning electron microscope, transmission
electron microscope, laser diffraction analysis and method of nitrogen absorption analysis.
2. Materials & Methods:
- A QM-DK low temperature planetary ball mill, 500 rpm for different times (1, 2 and 3 h). The starch samples and
five times weight ceramic balls.
- The X-ray diffraction analysis was performed using a Rigaku D/max-2500 V diffractometer, The FTIR spectra of
starches with different milling times were recorded on Avatar 360, High-resolution solid-state 13C CP/MAS
experiments were conducted using Bruker 300 ultrashieldTM.
- Scanning electron microscope (SEM), Laser diffraction analysis: Malvern Mastersizer, Transmission electron
microscope (TEM), Pore size distribution: surface area basing on BET adsorption isotherm. The pore size
distribution was obtained applying the iterative method of Barret, Joyner and Hallendy (BJH).
3. Results:
- The X-ray diffraction patterns (Fig 1), all the diffraction peaks at 2 h and 3 h almost disappeared, reflected the
decrease of crystallinity, which was the result of the transition from polycrystalline state to amorphous state ( table
2). Destruction of crystalline area and promotion of the amorphous area in the starch granules.
- (Fig 2.)the intensities of bands at 3382 cm1 and 1018 cm1 in the treated starch spectra were increased with
the increase of milling time, and the band (1047 cm1) was almost resolved at 1 h ball milling treatment, at the
same time, the amplitude of band (995 cm1) was decreased with the milling time.
- 13C CP/MAS NMR (Fig 3), shifts in peaks. his resolution of triplet peak was believed to decrease of double helix
content in ball milled starches
- (Fig 4) Significant changes in the internal structure of the granule. For 2 h the integrity and granule periphery still
remained.
- milling treatment from 0 to 2 h was growth process of the particle size, and particle size decreases occurred with
longer milling time (3 h). Fig 6: starch had lost its inherent granule characteristics (morphology,
crystalline structure and integrity). Fig 7: Hysteresis loop of ball milled starch (2 h) was larger than that of
untreated starch.
- SBET or the VBJH and DBJH were increased. It was indicated that mesopores and macropores existed in the
inner of starch granules beside microspores on the surface of granules. (2 h) gave a wider pore diameter
distribution (1355 nm), whereas untreated maize starch showed a narrow distribution of pore diameters (1035
nm)
4. Conclusion
- Decrease in double helix content and crystalline component of maize starch. Meanwhile, span and median
diameter, special surface area (SBET), cumulative volume (VBJH) and average diameter pores (DBJH) of starch
granules increased rapidly.
- increase greatly the porosity of starch, which indicated that ball milling treatment can induce the adsorptive capacity
of starches.