Modification and adsorption performance of ultrafine iron matrix composite powder
-
Li Zhang
,
Yao Ding
Abstract
Ultrafine matrix composite powder was prepared from brown corundum slag, grinding balls, anhydrous ethanol, and modifier using a planetary ball mill. The adsorption material was used for dyeing wastewater treatment. A pH instrument, spectrophotometer, and digital water bath oscillator were used to study the amount of modifier, milling speed, milling time, ball-to-powder weight ratio, and slurry concentration to investigate the effects of preparation conditions on the adsorption performance of adsorbent material. The prepared adsorbents and activated carbon were used to adsorb methylene blue in solution under the same conditions to compare adsorbent dosage, adsorption time, temperature, pH of solution, and initial concentration of methylene blue and to study their effects on methylene blue decolorization rate. The experiment results show that dosage of R of 7.5%, ball-to-powder weight ratio of 14:1, rotational speed of 500 rpm, slurry concentration of 20%, and ball milling time of 2.5 h were the optimum parameters. The composite powder (4 g/l) was added to methylene blue wastewater (35 mg/l), pH was adjusted to 6, and adsorption was carried out for 0.5 h at 30°C. The removal rate reached 99.4%.
1 Introduction
Currently, brown corundum slag is mainly used for extracting ferrovanadium [1] and ferrophosphorus [2], as a metallurgical addition agent [3], and for making fire-resistant materials [4]. Vast amounts of brown corundum slag not only occupy farmland but also cause severe pollution to the surrounding environment. Because we could not tap its potential utilization value, research on its further processing as environmental adsorption material has not been done.
R is a natural material consisting of Al2O3, SiO2, Fe2O3, CaO, and other ingredients. It is strongly hydrophilic, expansive, has suspension property, and so on, which makes it poorly capable of adsorbing organic compounds in wastewater and thus directly influencing its practical application.
An ultrafine iron matrix composite powder (UIMCP) was prepared from brown corundum slag using mechanical-chemical modification. Its adsorption properties for reactive dyes were investigated to broaden the utilization field of brown corundum slag and to develop the resources of adsorption material with high additional value.
The nature of the chemical modification of the mechanical force is the conversion of mechanical energy to chemical energy, which implements the combination of ultrafine grinding and surface organic modification, such as by the action of mechanical force (pulverization, impact, grinding, etc.), to improve the surface characteristics of the particles, to change the solubility of the crystal structure, etc. The physical and chemical effects that occur on the particle surface of the activation point and the modifying agent were studied to promote uniform distribution of the modifying agent on the powder surface and achieve the purpose of the modification [5].
In the ball milling method, brown aluminum oxide slag is added to the ball mill tank, together with grinding balls, anhydrous ethanol, and modifier, using the ball milling speed and ball milling time required to modify the adsorption material.
This experiment attempts to seek a use for brown corundum slag and make a new iron-based composite of ultrafine powders as an adsorption material for dyeing wastewater treatment; it can also broaden its using domain and improve raw material with high additional value.
An orthogonal experiment (Taguchi method) was used to seek the optimum experimental conditions.
2 Materials and methods
The instruments used were a planetary ball mill (Nanjing University Instrument Factory, QM-3SP04 type, Nanjing, China), spectrophotometer (Prius Tianjin Instrument Co., Model 721, Tianjin, China), pH instrument (Shanghai Precision Instruments Co., PHS-25 type, Shanghai, China), surface area and pore size analyzer (USA Quantachrome Instruments, NOVA2000e, USA), and a scanning electron microscope (JSM-5510LV, Japan).
Reagents used were ethanol (AR, Tianjin Bodie Chemical Company, Tianjin, China), methylene blue (BS, Shanghai Ace Reagent Company, Shanghai, China), concentrated sulfuric acid, and concentrated hydrochloric acid (AR, East of Kaifeng Group Zhongping, Kaifeng, China).
The raw material was brown corundum slag (Wuhan, China) from Wuhan Iron and Steel Group. Its main component is iron and has the following composition: Fe2O3, 70–75%; Al2O3, 7.2–11.5%; SiO2, 3.4–5.6%; TiO2, 3.2–4.8%, and others.
2.1 Brown alumina slag pretreatment
The brown alumina slag was broken into small pieces with a crusher, and then the raw material was passed through a 150-mesh sieve to remove stones, sand, and other impurities; recovery was more than 95%. Then the sifted brown alumina slag was placed in a digital drum wind dryer at a temperature of 120°C for 6 h. Brown alumina slag was taken out to cool, placed in a desiccator, weighed for a certain quality to place in a ball mill tank.
2.2 R pretreatment
R was passed through a 150-mesh sieve to remove large particles; the recovery was more than 99%. Then R was placed in a digital drum wind-drying machine at a temperature of 120°C to dry for 4 h and then transferred to the dryer cooling backup.
The specific steps are as follows:
Compound paste: To the ball mill tank was added grinding balls, modifier, and anhydrous ethanol according to a certain proportion, the mixture was stirred to obtain a certain concentration of slurry, and the ball grinding paste temperature was determined.
Modification: The ball mill pot in the ball mill, according to the predetermined parameters of ball milling time and speed of ball mill modification time. The slurry temperature of ball mill tank was measured immediately after the ball milling modification.
Filtering and drying: The size of the circulating water type vacuum pump filter was modified. The modified samples were placed in the digital drum wind dryer at constant temperature of 80°C to dry for 2 h, cooled to room temperature, and then passed through a 200-mesh sieve to modify the samples. The vacuum suction filtration filtrate was recycled.
The ball used was a milling ball, the ball mill can and vial were agate, the ball diameter is the milling ball diameter, the volume of vial is equal to the volume of the ball milling can, that the weight of the materials in the vial is the quality of the brown alumina slag, grinding balls, modifier R and anhydrous ethanol in the ball mill tank.
A certain amount of UIMCP material was placed into the methylene blue wastewater and pH was adjusted. After shaking in a water bath at a certain temperature and time, the absorbance (λmax=665 nm) of methylene blue was measured.
3 Results and discussion
3.1 Determination of the preparation conditions of UIMCP material
3.1.1 Effect of dosage of R on modification
UIMCP material was prepared at the ball-to-powder weight ratio of 4:1, milling time of 0.5 h, speed of 450 rpm, and slurry concentration of 25%. The effect of different dosages of R on the modification result was discussed.
Figure 1 shows that with the increase in R content, the decolorization rate of UIMCP material on methylene blue increased gradually. R dosage of 8% gave the best decolorization effect; the decolorization rate reached 95.4%. At increasing R dosage, decolorization rate decreased. The reason is that mechanical force activation is induced, R is stripped into tiny single chips, specific surface area also increase, and in the formation of brown fused alumina slag surface coating was observed. The mechanochemical effect not only results in the size of R pellets, but also results in coating of the material surface. When the R content increased gradually to 8%, the material was coated completely. When the amount of R was continually increased (>10%), the original coating layer was coated with R again, which decreased the UIMCP specific surface area and reduced adsorption performance. Thus, the optimum dosage of R is 8%.
Effect of dosage of R on modification.
3.1.2 Effect of the ball-to-powder weight ratio on modification
UIMCP material was prepared at the dosage of 8%, milling time of 0.5 h, speed of 450 rpm, and slurry concentration of 25%. The effect of different ball-to-powder weight ratios on the modification result is discussed.
Figure 2 shows that with increase of the ball-to-powder weight ratio, the removal rate increased first and then decreased. When the ball-to-powder weight ratio is 12:1, the removal rate reaches a maximum (98.4%). When the ball-to-powder weight ratio is too high, decolorization rate gradually decreased. This is because the ball-to-powder weight ratio is relatively small (<10:1) and the material has less chance of receiving mechanical force from the ball, which decreases material surface activity and specific surface area. When the ball-to-powder weight ratio is too large (>14:1), the ball mechanical force is too strong, which makes the cladding layer peel off and reduces the adsorption performance. Thus, 12:1 is the best ball-to-powder weight ratio.
Effect of the mass ratio of ball and powder on modification.
3.1.3 Effect of rotational time on modification
UIMCP material was prepared at the dosage of 8%, the ball-to-powder weight ratio of 12:1, speed of 450 rpm, and slurry concentration of 25%. The effect of different rotational times on the modification result is discussed.
Figure 3 shows that with the increase in the milling time the adsorption material increases at first and then decreases and reaches a maximum value of 99.1% at 120 min. In the early stage of the reaction, the milling time is shorter and R function is not fully modified, leading to a not so high adsorption performance. Along with the increase in ball milling time, 120 min is required for the material surface to be completely covered. As the milling time is continually increased (>150 min), the mechanical force leads powder agglomeration, which reduces adsorption performance.
Effect of rotational time on modification.
3.1.4 Effect of rotational speed on modification
UIMCP material was prepared at the dosage of 8%, ball-to-powder weight ratio of 12:1, milling time of 2.0 h, and slurry concentration of 25%. The effect of different rotational speed on the modification result is discussed.
From Figure 4, at the 300–450 rpm range, UIMCP material adsorption performance gradually increased with milling speed increase and was best at 450 rpm and above. Grinding ball motion increased, mechanochemical effect per unit time was enhanced, material specific surface area is larger, coating modification was more fully enhanced. When the speed is too high (>500 rpm), the mechanochemical effect is too strong, leading to the cladding layer peeling off and reducing the adsorption performance. Therefore, the selected ball mill speed is 450 rpm.
Effect of rotational speed on modification.
3.1.5 Effect of slurry concentration on modification
UIMCP material was prepared at the dosage of 8%, ball-to-powder weight ratio of 12:1, milling time of 2.0 h, and speed of 450 rpm. The effect of different slurry concentrations on the modification result is discussed.
Figure 5 shows that when the slurry concentration is 20%, adsorption performance is best, showing that R modification effect is best. When the slurry concentration is too high (>25%), the dispersion of powder is reduced, liquidity weakens, and the mechanochemical effect produced by the milling ball is weakened: High pulp density accelerated the agglomeration of powder, thus reducing the adsorption performance. Thus, the optimum slurry concentration is 20%.
Effect of slurry concentrations on modification.
To sum up, the optimum ball milling parameters were determined: At R content of 8%, ball-to-powder weight ratio of 12:1, milling time of 2 h, speed of 450 rpm, and slurry concentration of 20%, the removal rate reached 99.6%.
3.1.6 Taguchi method
The Taguchi experiment design uses orthogonal table selection of experimental conditions and arrangements of the experimental method.
The effects of factors like R content, milling time, milling speed, ball-to-powder weight ratio, and other factors on the modification are complex. This experiment selects four factors and three levels for the orthogonal experiment to test the prepared UIMCP materials’ adsorption performance. Table 1 shows the factors and levels and Table 2 presents the results of the adsorption experiments.
Factor levels for orthogonal experiment.
| Level | Dosage of R (%) | Ball-material ratio | Milling time (min) | Milling speed (rpm) |
|---|---|---|---|---|
| A | B | C | D | |
| 1 | 7.5 | 10:1 | 90 | 400 |
| 2 | 8.0 | 12:1 | 120 | 450 |
| 3 | 8.5 | 14:1 | 150 | 500 |
Results of orthogonal experiment and analysis.
| Number | Factor | Removal rate (%) | |||
|---|---|---|---|---|---|
| Dosage of R (%) | Ball-material ratio | Milling time (min) | Milling speed (rpm) | ||
| 1 | 7.5 | 10:1 | 90 | 400 | 99.88 |
| 2 | 7.5 | 12:1 | 120 | 450 | 99.54 |
| 3 | 7.5 | 14:1 | 150 | 500 | 99.94 |
| 4 | 8 | 10:1 | 120 | 500 | 99.67 |
| 5 | 8 | 12:1 | 150 | 400 | 99.45 |
| 6 | 8 | 14:1 | 90 | 450 | 99.25 |
| 7 | 8.5 | 10:1 | 150 | 450 | 99.70 |
| 8 | 8.5 | 12:1 | 90 | 500 | 99.84 |
| 9 | 8.5 | 14:1 | 120 | 400 | 99.77 |
| K1 | 99.85 | 99.75 | 99.63 | 99.61 | |
| K2 | 99.47 | 99.72 | 99.72 | 99.55 | |
| K3 | 99.77 | 99.66 | 99.79 | 99.84 | |
| R | 0.029 | 0.003 | 0.007 | 0.018 | |
Table 2 presents the IMCP material modification agents K1–K3, ball-to-powder weight ratio, milling time, speed, and four factors corresponding to each level of IMCP material preparation decolorization rate average. Table 2 shows that the dosage of R to the UIMCP material could have a greater impact on removal rate than speed, time, and the ball-to-powder weight ratio.
Thus, single-factor and orthogonal experiments determined that the best IMCP material preparation parameters were as follows: R dosage of 7.5%, ball-to-powder weight ratio of 14:1, ball milling time of 2.5 h, speed of 500 rpm, and slurry concentration of 20%; the removal rate reached 99.94%.
3.2 Condition of material adsorption of methylene blue wastewater
The factors that might influence the adsorption performance of UIMCP were investigated, such as adsorbent dosage, adsorption time, temperature, and pH value, using the UIMCP material prepared under the optimum condition.
3.2.1 Effect of adsorption dosage on adsorption performance
The effect of different dosages of adsorption material on adsorption performance was studied under the following conditions: temperature, 25°C; pH 6; initial concentration of methylene, 35 mg/l; adsorption, 30 min; and a shaker speed of 150 rpm.
Figure 6 shows that when adsorbent dosage increased from 1 to 4 g/l, IMCP material decolorization rate rapidly increased from 68.8% to 99.1%, and activated carbon grain content increased from 68.8% to 90.1%. Because the concentration of methylene blue is fixed, as the adsorbent dosage increased, the specific surface area and adsorption sites increased rapidly. The adsorption budge is reached with the UIMCP dosage of 4 g/l, its removal rate is 99.1%, but activated carbon content is only 90.1%. However, as adsorbent dosage continues to increase, material adsorption performance rises significantly. This is because that, under the condition that the volume of the solution is constant, increasing amount of adsorbent means that the decrease of the amount of adsorption unit. Continually increasing the dosage of adsorbent reduces unit absorbance as well as adsorption performance. In the same dosage, achieving the same decolorization rate, UIMCP material usage is nearly 10% less than that of activated carbon particles.
Change in removal rate by different use level of modifier.
3.2.2 Effect of adsorption time on adsorption performance
Effects of different adsorption times on adsorption performance were studied under the following conditions: adsorption dosage, 4 g/l; temperature, 25°C; pH 6; initial concentration of methylene, 35 mg/l; and a shaker speed of 150 rpm.
Figure 7 shows that the decolorization rate of two kinds of adsorbent for adsorption of methylene blue varies with increasing adsorption time. The adsorption time is 15 min, methylene blue decolorization rate with IMCP material reached 99.1%, and activated carbon granule content is 90.1%. When the adsorption time reaches 30 min, the curve tends to balance, showing that adsorption balance is reached at the adsorption time of 30 min. Under the same experimental conditions activated carbon adsorption of methylene blue has the following characteristics: In the initial 5 min, removal rate of UIMCP can reach 96.48% and activated carbon particle content is only 72.4%. At 30 min, the adsorption reaches equilibrium and decolorization rate of UIMCP is 99.5%; however, the activated carbon content is only 91.8%, more than 7.7% decrease. The results show that compared to activated carbon particles, the UIMCPs have the characteristics of quicker adsorption rates and higher adsorption efficiency.
Change in removal rate by different time.
3.2.3 Effect of temperature on adsorption performance
The effects of different temperatures of adsorption material on adsorption performance were studied under the following conditions: adsorption dosage of 4 g/l; pH 6; initial concentration of methylene, 35 mg/l; adsorption time, 30 min; and a shaker speed of 150 rpm.
Figure 8 shows that in the temperature range of 15–30°C, methylene blue decolorization rate increases with temperature. The rise in temperature speeds up the molecular thermal motion of the solution system, making the methylene blue and adsorbent molecules increase contact with each other and thus increase adsorbent adsorption efficiency through an endothermic process. When the temperature is 30°C, the maximum removal rate of UIMCP reaches 99.4%. When the temperature continues to increase (>30°C), methylene blue removal rate decreases from 99.4% to 97.2%. In this range, the influence of temperature on the adsorption is a negative effect. Therefore, methylene blue adsorption on the iron-based superfine powder composite materials is the first endothermic process after the process of heat release. Decolorization rate of methylene blue adsorbed on activated carbon granules increases with temperature rise, and activated carbon particle content reaches 91.2% at 40°C. When the temperature continues to increase, decolorization rate decreases. At a certain temperature range, increasing temperature is in favor of adsorbent; at too high temperature, methylene blue stripping and decolorization rate decrease. The results show that UIMCP material has a wider temperature adaptiveness (20–50°C) than activated carbon particles.
Change in removal rate by different temperature.
Figure 9 shows the methylene blue adsorption isotherms at different temperatures.
Adsorption isotherm of methylene blue.
The adsorption isotherms were fitted by using Langumir equation [6] and Freundlich equation [7]. Table 3 shows the fitted results. Table 3 shows that adsorption of methylene blue on the surface of UIMCP is correlated with the Langmuir isotherm, and it produces a monolayer adsorption. The maximum adsorption capacity was 26.49 mg/g.
Summary of the isotherm constants and the correlation coefficients for different isotherms.
| Langmuir equation | Freundlich equation | |||
|---|---|---|---|---|
| qmax/(mg/l) | b (l/mg) | R2 | 1/n | R2 |
| 26.49 | 0.0379 | 0.9996 | 0.2994 | 0.8898 |
3.2.4 Effect of pH value on adsorption performance
The effects of different pH values of adsorption material on adsorption performance were studied under the following conditions: adsorption dosage, 4 g/l; temperature, 25°C; initial concentration of methylene, 35 mg/l; adsorption, 30 min; and a shaker speed of 150 rpm.
Figure 10 shows that when the pH value of the solution ranges from 3 to 6, the IMCP material decolorization rate increases with increase in pH value. This is because in acid medium the R surface is negatively charged with electricity, and there is H+ and methylene blue cation competitive adsorption. With the reduction of the concentration of H+, IMCP materials enhance the exchange adsorption for methylene blue treatment. When the pH value is greater than 7, the removal rate decreases. The reason is that in alkaline medium, there is competitive adsorption between the R surface negative charge and OH-; methylene blue cations combine with OH-, which reduces the adsorption performance. Therefore, this study determined the optimal pH value as 6 due to the competitive adsorption of the R negative surface charge and OH-.
Change in removal rate by different pH.
The result shows that activated carbon granule adsorption of methylene blue and decolorization rate decrease with the pH value, larger pH value is not conducive for the granular of activated carbon adsorbed methylene blue. IMCP adsorption of methylene blue and decolorization rate was maintained at 98% and above; it is obviously superior to the activated carbon granule, whose highest decolorization rate is 92%. Compared to activated carbon particles, UIMCP material has a broad range of pH value from 3 to 9, and the removal rate is more than 98%.
3.2.5 Study on the adsorption kinetics
The adsorption kinetics of purified palygorskite for methylene blue from aqueous solutions was investigated.
Figure 11 shows that methylene blue adsorption on UIMCP material is a quick process. Ninety percent methylene blue was adsorbed, and adsorption equilibrium was reached within 30 min. Rapid kinetic adsorption is mainly due to the UIMCP material’s pore structure and specific surface area, which provides a very fast transfer speed for the methylene blue during the adsorption process and accelerates the rate of adsorption.
Change in removal rate by different initial concentration.
In order to further understand the adsorption kinetics mechanism of UIMCP material for methylene blue, the adsorption isotherms were fitted by using a pseudo first-order equation [8] and a quasi two-stage equation [9]. Table 4 shows the fitted results.
Adsorption kinetic parameters of methylene blue.
| C0 (mg/l) | Pseudo first-order equation | Pseudo second-rate equation | ||
|---|---|---|---|---|
| ln (Qe-Qt)=ln Qe-K1t | t/Qt=1/(K2Qe2)+t/Qe | |||
| K1 | R2 | K2 | R2 | |
| 15 | -0.1799 | 0.9795 | 0.1329 | 0.9983 |
| 35 | -0.1526 | 0.9275 | 0.0568 | 0.9999 |
| 50 | -0.1894 | 0.9318 | 0.0403 | 0.9998 |
Qe, Qt, balanced adsorbing volume (mg/g): K1 and K2 (per min), sorption rate constants.
From Table 2 we can see that the adsorption behavior of methylene blue on the surface of UIMCP is correlated with a quasi two-stage adsorption kinetics mode. The adsorption for the methylene blue fits physical diffusion control to a certain degree.
3.3 Performance test for UIMCP material
3.3.1 SEM analysis
SEM micrographs of corundum slag and UIMCP material are shown in Figures 12 and 13, respectively. Figure 12 shows that the surface particles of brown corundum slag are of different sizes, loose, with larger gaps, and with a mean particle size of 1–5 μm. Figure 13 shows an SEM image of UIMCP material prepared under optimum technology conditions with the orthogonal experiment. After mechanical-chemical modification, the structure of UIMCP material is of “coated particle” type, with well-distributed particle size, average particle diameter of about 0.3 μm, and with more pore space and multichannels, which aids in adsorption.
SEM image of corundum slag.
SEM images of different materials (dosage of R, 7.5%; mass ration of ball, 14:1; rotational time, 150 min; rotational speed, 500 rpm; slurry concentration, 20%).
3.3.2 Analysis of surface area and pore structure
N2 isothermal adsorption-desorption curves of UIMCP materials prepared under different rotational times were tested. N2 adsorption-desorption curves are shown in Figure 14A, and pore distribution is shown in Figure 14B.
N2 adsorption-desorption isotherms (A) and pore size distribution curves (B).
Figure 14A shows that UIMCP material isotherms are Langmuir IV – typical mesoporous materials characteristic of adsorption type [10] – and have an obvious hysteresis loop, which is composed of holes of uniform size and shape caused by holes and belong to typical mesoporous material adsorption removal with characteristic curve.
In Figure 14B and Table 5, the IMCP1–IMCP4 isotherms all belong to Langmuir type IV, namely, the typical mesoporous material characteristic of adsorption type [10], and has an obvious hysteresis loop, which is caused by the holes of regular size and shape, belongs to the typical mesoporous material adsorption a stripping characteristic curve, which explains why IMCP materials have a mesoporous structure. At low partial pressure (P/P0<0.45), N2 adsorption increases linearly with P/P0, the adsorption curve and stripping curve almost coincide, and there is no hysteresis loop. This is because the N2 in the hole wall produces monolayer adsorption. When the relative pressure P/P0 is >0.45, stripping phenomenon starts to appear, and there are obvious adsorption-stripping hysteresis loops. N2 in the channels of the capillary condensation adsorption has reached saturation mainly due to the skeleton formed mesoporous capillary condensation sake which illustrated materials also exist within the mesopores and macropores [11]. IMCP material hole radius is between 15 and 50 nm and belongs to the mesoporous structure. With increasing milling time, the surface area of UIMCP and pore volume assume the trend of escalation and reach the maximum at 150 min, specific surface area of 61.34 m2/g and pore volume of 0.074 cm3/g. The diameter of the material decreases from 19.263 to 18.923 nm, and mechanical activation induces dispersion of R in the mesoporous channels. With increasing milling time, the R is dispersed uniformly and pore size decreases gradually.
Pore structural characteristics of different materials.
| Sample | BET surface area (m2/g) | Pore volume (cm3/g) | Pore size (nm) |
|---|---|---|---|
| UIMCP1 | 5.79 | 0.033 | 19.263 |
| UIMCP2 | 11.17 | 0.034 | 19.096 |
| UIMCP3 | 49.95 | 0.063 | 18.954 |
| UIMCP4 | 61.34 | 0.074 | 18.923 |
4 Conclusions
According to the single-factor experiment and the orthogonal experiment, the conditions of UIMCP modification preparation and adsorption of methylene blue wastewater were determined as follows:
The optimum ball milling parameters are as follows: R dosage of 7.5%, ball-material ratio of 14:1, ball milling time of 2.5 h, speed of 500 rpm, and slurry concentration of 20%.
The optimum adsorption conditions for ethylene wastewater were adsorption dosage of 4 g/l, temperature of 25°C, pH 6, initial concentration of methylene 35 mg/l, adsorption 30 min, and a shaker speed of 150 rpm. Removal rate was 99.94%.
Compared to activated carbon particles, UIMCP materials had less usage, quick adsorption rates (15 min), a broad range of pH value from 3 to 9, wide temperature adaptiveness (20–50°C), and so on.
SEM analysis indicates the structure of ultrafine matrix composite powder as coated particle: N2 adsorption-desorption experiment demonstrates the surface area of material up to 61.34 m2/g and diameter of 18.923 nm.
The adsorption process follows Langmuir isotherm, and kinetics follows the mechanism of the pseudo second-order equation.
The authors are grateful to the support from the Wuhan Institute of Technology Engineering Center for Phosphorus and the Youth Foundation of Wuhan Institute of Technology.
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