Ultrasound assisted chrome tanning: Towards a clean leather production technology

Nowadays, there is a growing demand for a cleaner, but still effective alternative for production processes like in the leather industry. Ultrasound (US) assisted processing of leather might be promising in this sense. In the present paper, the use of US in the conventional chrome tanning process has been studied at different pH, temperature, tanning time, chrome dose and US exposure time by exposing the skin before tanning and during tanning operation. Both prior exposure of the skin to US and US during tanning improves the chrome uptake and reduces the shrinkage significantly. Prior exposure of the skin to US increase the chrome uptake by 13.8% or reduces the chrome dose from 8% to 5% (% based on skin weight) and shorten the process time by half while US during tanning increases the chrome uptake by 28.5% or reduces the chrome dose from 8% to 4% (half) and the tanning time to one third compared to the control without US. Concomitantly, the resulting leather quality (measured as skin shrinkage) improved from 5.2% to 3.2% shrinkage in the skin exposed to US prior tanning and to 1.3% in the skin exposed to US during the tanning experiment. This study confirms that US chrome tanning is an effective and eco-friendly tanning process which can produce a better quality leather product in a shorter process time with a lower chromium dose.     

Ultrasonic effects on titanium tanning of leather

The effects of ultrasound on titanium tanning of leather were investigated. Either 20 or 40 kHz ultrasound was applied to the titanium tanning of pigskins. Five different treatment conditions were carried out and the effects were examined, such as leather shrinkage temperature (T(s)), titanium content and titanium distribution in the leather. Overall heat loading was carefully controlled. Results showed that 20 kHz ultrasound effectively improves titanium agent penetration into the hide and increases the leather's shrinkage temperature. Doubling the frequency to 40 kHz produced negligible enhancements. An impressive 105.6 degrees C T(s) was achieved using 20 kHz ultrasound pretreatment of the tanning liquor followed by 20 kHz ultrasound in the tanning mixture (liquor plus pigskins) in a special salt-free medium. Finally, using a unique ultrasonic tanning drum with 26.5 kHz ultrasound, the T(s) reached a record level of 106.5 degrees C, a value not achieved in conventional (no ultrasound) titanium tanning. The ultrasonic effects on titanium tanning of leather are judged to make a superior mineral tanned leather.     

Sono-leather technology with ultrasound: a boon for unit operations in leather processing - review of our research work at Central Leather Research Institute (CLRI), India

Ultrasound is a sound wave with a frequency above the human audible range of 16Hz to 16kHz. In recent years, numerous unit operations involving physical as well as chemical processes are reported to have been enhanced by ultrasonic irradiation. There have been benefits such as improvement in process efficiency, process time reduction, performing the processes under milder conditions and avoiding the use of some toxic chemicals to achieve cleaner processing. These could be a better way of augmentation for the processes as an advanced technique. The important point here is that ultrasonic irradiation is physical method activation rather than using chemical entities. Detailed studies have been made in the unit operations related to leather such as diffusion rate enhancement through porous leather matrix, cleaning, degreasing, tanning, dyeing, fatliquoring, oil-water emulsification process and solid-liquid tannin extraction from vegetable tanning materials as well as in precipitation reaction in wastewater treatment. The fundamental mechanism involved in these processes is ultrasonic cavitation in liquid media. In addition to this there also exist some process specific mechanisms for the enhancement of the processes. For instance, possible real-time reversible pore-size changes during ultrasound propagation through skin/leather matrix could be a reason for diffusion rate enhancement in leather processing as reported for the first time. Exhaustive scientific research work has been carried out in this area by our group working in Chemical Engineering Division of CLRI and most of these benefits have been proven with publications in valued peer-reviewed international journals. The overall results indicate that about 2-5-fold increase in the process efficiency due to ultrasound under the given process conditions for various unit operations with additional benefits. Scale-up studies are underway for converting these concepts in to a real viable larger scale operation. In the present paper, summary of our research findings from employing this technique in various unit operations such as cleaning, diffusion, emulsification, particle-size reduction, solid-liquid leaching (tannin and natural dye extraction) as well as precipitation has been presented.     

Sono-oxidation treatment of humic substances in drinking water.

Currently humic substances are removed from the raw water prior to chlorination by the conventional coagulation and filtration method using aluminium sulphate. Application of high-intensity (> 10 W/cm2) ultrasonic irradiation in conjunction with oxidative process using commercial oxidants H2O2 was investigated as an alternative. Sono-oxidation and sonodegradation of natural and synthetic humic substances have been followed over time by measuring total organic carbon (TOC) and absorbance by ultraviolet spectrometer (UV-VIS). It took approximately 60 min to reduce TOC by half and to have a complete degradation of humic acid.     

Comparative study of lignins isolated by alkali and ultrasound-assisted alkali extractions from wheat straw.

Treatment of the dewaxed wheat straw with 0.5 M KOH at 35 degrees C for 2.5 h without ultrasonic irradiation and with ultrasound assistance for 5, 10, 15, 20, 25, 30, and 35 min resulted in a dissolution of 43.9%, 43.9%, 43.9%, 44.4%, 44.4%, 45.6%, 46.8%, and 49.1% of the original lignin, respectively. Much better results were achieved under the ultrasonic irradiation time for 35 min where nearly 50% of the original lignin was solubilized at 35 degrees C for 2.5 h. The purity of the lignin preparations isolated by alkali with ultrasound assistance was higher than that of the lignin fraction obtained by alkali without ultrasonic irradiation, and their purity increased with an increment of irradiation time between 5 and 35 min, in which the content of associated polysaccharides in the former lignin preparations (0.87-1.06%) was lower than that of the latter lignin fraction (1.16%). In addition, the lignins isolated by alkali with ultrasonic irradiation time between 5 and 30 min showed a slightly higher molecular weight and thermal stability than the lignin obtained by alkali without ultrasound assistance. No substantial differences in the main structure features between the lignin preparations isolated by alkali and ultrasound-assisted alkali extractions were found.     

Sonochemical effect and pore structure tuning of silica xerogel by ultrasonic irradiation of semi-solid hydrogel

Silica xerogels were prepared by the sol-gel method under ultrasonic irradiation, using tetraethylorthosilicate (TEOS) as the starting material. Hexamethyldisiloxane (HMDSO) was used as the hydrophobizing agent. When preparing silica xerogel, it is necessary to perform aging and hydrophobization to suppress shrinkage during ambient pressure drying, however, such treatments are time-consuming. In this study, the semi-solid hydrogel was irradiated with ultrasonic for the first time in order to accelerate aging and hydrophobic treatment, and the effect of ultrasonic frequency on structure was investigated. Firstly, ultrasonic irradiation was performed at frequencies of 100 kHz and 500 kHz, followed by hydrophobic treatment at a frequency of 500 kHz, in order to promote aging. The results identify optimum conditions for ultrasonic irradiation to promote aging and hydrophobization reactions, and it was found to be possible to prepare silica xerogels in less than 1/5 of the conventional time. The silica xerogels had a low density and the shrinkage was suppressed. In this study, it was found that ultrasonic irradiation of semi-solid hydrogel was very effective for promoting the reaction.     

Ultrasonic-assisted Dunlop method for natural rubber latex foam production: Effects of irradiation time on morphology and physico-mechanical properties of the foam

An ultrasonic-assisted technique was first introduced for the production of natural rubber latex foam (NRLF). The flexible elastomeric foam was formed by a liquid–solid state transformation in an aqueous media. The aim of the current research was to provide a novel strategy for fabricating NRLF using ultrasonication and the Dunlop method, as well as to simultaneously utilize irradiation events to achieve the desired foam properties. NRLFs were exposed to ultrasonication at 25 kHz at the beginning of the gelling process. The effects of irradiation times of 0, 1, 3, 5 and 7 min on the morphology, foaming behaviors, physical properties and mechanical performance of NRLFs were investigated. The results revealed that using ultrasonic irradiation, unfoamed regions and a bimodal structure, which seem to be microstructural defects in conventional NRLF, could be completely eliminated. However, excessive irradiation times of 5 min and longer appeared to affect the physico-mechanical properties of the foams in terms of transient cavitation and the unfavorable physicochemical effects of ultrasonic vibrations. As a result, the optimal ultrasonic irradiation time was found to be 3 min. Using this irradiation duration, a foam with the suitable microcellular structure achieved the most desirable properties, such as its expansion ratio (7-fold increase), foam porosity (85.7%), compression recoverability (98.7%), and tensile strength (307.3 kPa). Moreover, the foam still maintained its characteristic soft nature (hardness less than 100 N) with an indentation hardness of 71.9 N. Therefore, ultrasonic treatment introduced to the conventional Dunlop method is a potentially feasible technique since it improves the morphology and the physico-mechanical properties of NRLFs.     

Using low intensity ultrasound to improve the efficiency of biological phosphorus removal

Low intensity ultrasound can produce various effects on biological materials, such as stimulating enzyme activity, cell growth, biosynthesis, etc., which may improve the efficiency of enhanced biological phosphorus removal (EBPR). We adopt total phosphorus (TP) and dehydrogenase activity (DHA) as indicators to confirm the feasibility of applying low intensity ultrasound in EBPR. Single-factor experiments and orthogonal test were conducted in batch anaerobic/oxic (A/O) process simulation to study the influence of ultrasonic intensity and exposure time in the EBPR process. The results showed that the optimal ultrasonic parameters were 0.2 W/cm² and 10 min under which condition the TP concentration in the effluent was 35–50% lower than that of the control (without ultrasonic irradiation). Changes of sludge activities after ultrasonic irradiation were examined. The improvement of sludge activity by ultrasound took 4 h after irradiation to reach the peak level, when an increase above 50% of DHA has been achieved by ultrasonic irradiation, and the enhancing effects induced by ultrasound disappeared in 16 h after irradiation. A tentative mechanism of biological phosphorus removal enhancement stimulated by ultrasound was discussed based on these phenomena.     

Studies on the use of power ultrasound in leather dyeing

Uses of power ultrasound for acceleration/performing the chemical as well as physical processes are gaining importance. In conventional leather processing, the diffusion of chemicals through the pores of the skin/hide is achieved by the mechanical agitation caused by the paddle or drumming action. In this work, the use of power ultrasound in the dyeing of leather has been studied with the aim to improve the exhaustion of dye for a given processing time, to reduce the dyeing time and to improve the quality of dyed leather. The effect of power ultrasound in the dyeing of full chrome cow crust leather in a stationary condition is compared with dyeing in the absence of ultrasound as a control experiment both in a stationary as well as conventional drumming condition. An ultrasonic cleaner (150 W and 33 kHz) was used for the experiments. Actual power dissipated into the system was calculated from the calorimetric measurement. Experiments were carried out with variation in type of dye, amount of dye offer, temperature and time. The results show that there is a significant improvement in the percentage exhaustion of dye due to the presence of ultrasound, when compared to dyeing in absence of ultrasound. Experiments on equilibrium dye uptake carried out with or without ultrasound suggest that ultrasound help to improve the kinetics of leather dyeing. The results indicate that leathers dyed in presence of ultrasound have higher colour values, better dye penetration and fastness properties compared to control leathers. The physical testing results show that strength properties of the dyed leathers are not affected due to the application of ultrasound under the given process conditions. Apparent diffusion coefficient during the initial stage of dyeing process, both in presence and in absence of ultrasound was calculated. The values show that ultrasound helps in improving the apparent diffusion coefficient more for the difficult dyeing conditions such as in the case of metal-complex dyes having bigger aggregate size compared to less difficult dyeing conditions.     

Ultrasonic de-agglomeration of barium titanate powder

BaTiO3 (BT) powder, with average particle size of 1.4 microm, was synthesized by solid-state reaction. A high-intensity ultrasound irradiation (ultrasonication) was used to de-agglomerate micro-sized powder to nano-sized one. The crystal structure, crystallite size, morphology, particle size, particle size distribution, and specific surface area of the BT powder de-agglomerated for different ultrasonication times (0, 10, 60, and 180 min) were determined. It was found that the particles size of the BT powder was influenced by ultrasonic treatment, while its tetragonal structure was maintained. Therefore, ultrasonic irradiation can be proposed as an environmental-friendly, economical, and effective tool for the de-agglomeration of barium titanate powders.     

Influence of ultrasonic waves in the reduction of nitrate to nitrite by hydrazine-Cu(II)

Colorimetric methods are still important for determining nitrate and nitrite. A critical step in the use of these methods to determine nitrate in low concentrations is the reaction time required to totally reduce nitrate to nitrite, i.e., 24h in the dark. This work involved a study of the influence of ultrasonic irradiation on the nitrate reduction reaction by hydrazine. Our findings indicated that ultrasonic irradiation, associated with copper(II) ion as a catalyst, increased the redox reaction rate, decreasing the reaction time to about 10min when the power of the ultrasonic irradiation was set in 14.0357W. The strong influence of the ultrasonic irradiation in the reduction reaction rates can be sustained by an excellent linear correlation (R(2)=0.9993) between the kinetic constants and ultrasonic powers. Nitrate conversion also increased from 68% to 98% at the latter conditions. It thus become clear that high intensity ultrasound is very beneficial for this reduction reaction to proceed in good yield and in short reaction time in comparison to its silent reaction.     

Ultrasound-enhanced extraction of lignin from bamboo (Neosinocalamus affinis): characterization of the ethanol-soluble fractions

Bamboo was submitted to ultrasound-assisted extraction in aqueous ethanol to evaluate the effect of ultrasonic irradiation on the dissolution of lignin. In this case, the dewaxed bamboo culms were subjected to ball milling for 48 h, and then were suspended in 95% ethanol followed by ultrasonic irradiations for varied times at 20 °C to obtain ethanol-soluble fractions. The structural and thermal properties of the ethanol-soluble fractions were comparatively investigated by chemical analysis including alkaline nitrobenzene oxidation, bound carbohydrate determination, FT-IR spectra, HSQC spectra, TG, and DTA. The results showed that the yields of the ethanol-soluble fractions were between 4.29% and 4.76% for the fractions prepared with ultrasonic irradiation time ranging from 5 to 55 min, as compared to 4.02% for the fraction prepared without ultrasonic irradiation. It was found that the lignin content of the fraction increased with the increase of the ultrasonic irradiation time. There was a slight increase of the molecular weight of the lignin with the increase of the ultrasonic irradiation time. Alkaline nitrobenzene oxidation coupled with HSQC analysis indicated that the lignin in the fractions was mainly composed of G S H type units as well as minor amounts of ferulic acids. In addition, the fraction prepared with ultrasonic irradiation exhibited a slightly higher thermal stability as compared to the fraction prepared without ultrasonic irradiation.     

A novel method for the preparation of III-V semiconductors: sonochemical synthesis of InP nanocrystals

A novel method for the preparation of III–V semiconductor has been provided in this paper. At room temperature, InP nanocrystals with diameter of ≈9 nm were successfully obtained under high-intensity ultrasonic irradiation for 4 h from the reaction of InCl₃·4H₂O, yellow phosphorus and KBH₄ in the mixed solvents of ethanol and benzene. Changing some parameters can effectively control the size of the products and possible explanations were offered. The products were characterized by X-ray powder diffraction, transmission electron microscope and electron diffraction pattern. The ultrasonic irradiation and the solvents are both important in the formation of the product.     

Ultrasound-assisted oxidative process for sulfur removal from petroleum product feedstock

A procedure using ultrasonic irradiation is proposed for sulfur removal of a petroleum product feedstock. The procedure involves the combination of a peroxyacid and ultrasound-assisted treatment in order to comply with the required sulfur content recommended by the current regulations for fuels. The ultrasound-assisted oxidative desulfurization (UAOD) process was applied to a petroleum product feedstock using dibenzothiophene as a model sulfur compound. The influence of ultrasonic irradiation time, oxidizing reagents amount, kind of solvent for the extraction step and kind of organic acid were investigated. The use of ultrasonic irradiation allowed higher efficiency for sulfur removal in comparison to experiments performed without its application, under the same reactional conditions. Using the optimized conditions for UAOD, the sulfur removal was about 95% after 9 min of ultrasonic irradiation (20 kHz, 750 W, run at 40%), using hydrogen peroxide and acetic acid, followed by extraction with methanol.     

压力下Nd60Al10Fe20Co10块体金属玻璃的弹性行为

室温下在等静压最高达～0.5GPa的条件下，利用超声回波技术测量了超声波横波和纵波在Nd₆₀Al₁₀Fe₂₀Co₁₀块体金属玻璃中的传播时间来确定横波和纵波速度.测量时所采用的超声波频率为10MHz.利用所测量的数据，建立了超声波波速、样品的密度、弹性模量以及Debye温度等与所施加的压力之间的相互关系.并且推导出Murnaghan状态方程.另外，基于非晶态与晶态物理性能的相似性，对此块体非晶的压缩曲线、弹性常数和Debye温度等进行了理论计算，结果表明Nd₆₀Al₁₀Fe₂₀Co₁₀块体金属玻璃的弹性性能与其组成的元素有着密切的关系. 关键词： 块体金属玻璃 弹性性能 等静压     

利用先验估计自适应加窗的准静态超声弹性成像位移估计算法

准静态弹性成像技术是基于组织压缩前和压缩后超声回波射频信号进行组织运动重构的弹性成像技术。提出了一种基于先验估计的自适应窗函数算法,在位移估计过程中,使用已估计的临近窗的时延值作为先验信息,自动调整截取压缩后射频信号段的截取窗函数,提高了互相关运算所需的压缩前和压缩后信号段之间的相关性。仿真实验结果表明,该算法不仅大大提高了成像速度,而且提高了信噪比较低时的成像质量,同时该算法具有更宽的应变通带。      

A new development of dyestuffs degradation system using ultrasound

Dyestuffs are often present in industrial wastewaters and can consist of hazardous substances which have a serious impact on the environment and personal health. This report describes a system developed to degrade these substances using sonochemical reactions. Ultrasonic frequencies of 118, 224, 404 and 651 kHz and power input values of 11.4, 29.0 and 41.5 W were tested on Rhodamine B and Orange II dyestuff solutions in order to find the best degradation conditions. The ultrasonic irradiation of air-saturated solutions produces free radicals that combine and generates hydrogen peroxide, and compared to the production of hydrogen peroxide when irradiating water, a decrease was found during the irradiation to dyestuff solutions, indicating that some of the free radicals were consumed in the dyestuffs degradation process. The effects of the ultrasonic irradiation conditions on the pH, nitric and nitrous acid formations as well as the total organic carbon value (TOC) were also investigated. For the ultrasonic frequencies of 224, 404 and 651 kHz, the degradation rates were very similar, however, the 118 kHz system presented a degradation rate of about one-third that of the higher frequencies for both dyestuffs. The Rhodamine B solutions were decolorized within 2 h of ultrasonic irradiation for all systems with the exception of the 118 kHz one. For Orange II, except for the 118 kHz system, all solutions were decolorized within 4 h of ultrasonic irradiation. All reactions were carried out at 25 degrees C and the total ultrasonic irradiation time was 10 h.     

电子束辐照浓香型白酒催陈效果的研究

以能量为1.5 MeV/u,剂量分别为500,750,1000,1250,1500 Gy的电子束对1,2,4,6,8年等5种年份浓香型白酒进行辐照处理;扫描各酒样200～400 nm波段的紫外光谱,根据紫外光谱图的差异,计算了280～300 nm波段的光谱曲线相似度,分析光谱曲线变化规律。结果表明,对于前4种白酒,对照样与辐照样光谱曲线相似度值越小,催陈效果越好;白酒存放时间越久,酒体风格转向老熟所需剂量越小,越容易达到最佳催陈效果;对于8年白酒,辐照剂量超过750 Gy后,白酒体系动态平衡被打破,各单体物质增加,出现返生现象。因此,电子束辐照技术对低年份浓香型白酒催陈效果显著,是一种先进、高效的催陈方法。     

Theoretical and experimental investigation of desalting and dehydration of crude oil by assistance of ultrasonic irradiation

In this paper desalting/dehydration process of crude oil by ultrasonic irradiation in a novel batch standing-wave resonator reactor is studied both theoretically and experimentally. The effect of main parameters including ultrasonic irradiation parameters, namely irradiation input power and irradiation time, and also operating parameters, such as temperature and injected water, on the removal efficiencies of salt and water is examined. The obtained results demonstrate that finding the optimum values of the above mentioned parameters is important to prevent a significant decrease in the removal efficiencies of water and especially salt. Thus, crude oil was subjected to optimal ultrasonic irradiation with an input power of 57.7 W, and irradiation time of 6.2 min at temperature of 100 °C. The injected water to dissolve the salt of crude oil was 7 vol.%. Also, the applied settling time and dosage of chemical demulsifier were 60 min and 2 ppm, respectively. Under these optimum conditions the removal efficiencies of the desalting/dehydration process were 84% and 99.8%, respectively, which are suitable for refineries.Also, based on the optimal experimental data, two inferential estimators are developed to obtain the relationships between the salt and water removal efficiencies, and input energy density. These empirical relationships can offer a proper estimation for the salt and water removal efficiencies with irradiation input energy.     

Purification of serratiopeptidase from Serratia marcescens NRRL B 23112 using ultrasound assisted three phase partitioning

The ultrasound assisted three phase partitioning (UATPP) is a novel bioseparation method for separation and purification of biomolecules. In the present work, UATPP was investigated for the first time for purification of serratiopeptidase from Serratia marcescens NRRL B 23112. Effect of various process parameters such as ammonium sulphate saturation, t-butanol to crude extract ratio, pH, ultrasonic frequency, ultrasonic intensity, duty cycle and irradiation time were evaluated and optimized. The optimized conditions were found to be as follows: ammonium sulphate saturation 30% (w/v), pH 7.0, t-butanol to crude ratio 1:1 (v/v), ultrasound frequency 25 kHz, ultrasound intensity 0.05 W/cm², duty cycle 20% and irradiation time 5 min. The maximum purity and recovery obtained from UATPP was 9.4-fold and 96% respectively as compared to the three phase partitioning (TPP) (4.2-fold and 83%). Also the process time for UATPP was significantly reduced to 5 min from 1 h as compared to TPP. The results indicate that, UATPP is an efficient technique for the purification of serratiopeptidase with maximum purity, recovery and reduced processing time.