Near infrared reflectance spectroscopy as a tool for the control of sheep leather defatting

The fat content is one of the variables to be controlled by the tanning industry with a view to obtaining leather for various commercial purposes. Ensuring the production of quality leather products frequently entails using some defatting treatment, particularly when the raw skin is rich in natural fat. The official method for determining fat in leather, IUC 4, is rather slow; also, it uses polluting reagents and involves powdering samples for Soxhlet extraction with low-polarity solvents. The combination of NIR diffuse reflectance spectroscopy as implemented with a fibre-optic probe and multivariate calibration is probably the best choice for the direct determination of fat in leather and the monitoring of leather defatting.In this work, a method for the determination of fat in leather and the control of the defatting process in an expeditious manner and with no sample treatment was developed. Defatting tests were conducted on leather specimens from lambs of various breeds and origins in order to span as wide as possible a range of variability in their properties and natural fat content. The NIR spectra used to construct the calibration matrices were recorded directly on the leather samples prior to and after defatting. Fat contents were determined by partial least-squares regression (PLSR), using the values obtained with the official method as references. Notwithstanding the complex nature of leather, the calibration models used provided good external predictions: the largest overall relative error, obtained by using a single calibration matrix for natural and defatted specimens, was 10%. The proposed method is therefore an advantageous alternative to the official method.     

The Interaction between Collagen and an Aluminum Tanning Agent

The interaction between collagen and organometallic aluminum complexes was studied. From the analysis of the IR and UV spectra, the viscosity of collagen, and the treated collagen, a possible interaction model of the collagen with the aluminum tanning agent has been found. It indicates that such an aluminum tanning agent could be used as a cleaner tanning agent in leather tanning.

Viscosity curves of the untreated collagen solution (a) and the collagen solution treated with aluminum tanning agent (b).     

Preparation and Application of a Nanocomposite (MPNS/SMA) in Leather Making

Environmental pollution is one of headache problems in leather tanning industry.Traditionally chrome tanning was the predominant technique used in leather making.However,chrome tanning is being substituted due to its pollution and scarcity of resource.The study of non-chrome tanning in leather shows more interests with the development of nanomaterial and nanotechnology.J.Z.Ma et al.have reported that organic–montmorillonite nanocomposite can raise the shrinkage temperature of pickled pigskin…     

Analysis of plasma-polymerized hydrocarbons by pyrolysis/gas chromatography

Plasma-polymerized oils, films and powders obtained from ethylene, acetylene, butadiene, and benzene were characterized by flash pyrolysis and gas chromatography (P/GC). None of the pyrograms resembled those of commercial polyethylene, polybutadiene, or polystyrene. Each of the plasma-polymer pyrograms did exhibit essentially the same fragments up to C₈, albeit in a different distribution, indicating that all samples are structurally similar. Analysis of the P/GC data shows these materials to contain a random arrangement of side chains, crosslinks, double bonds, and aromatic structures. Changes in the fragment distribution were obvious when the sample was a powder, solid film, or oily film produced from the same monomer. It was shown that powder products generally have a higher concentration of branches and/or crosslinks than the oil or film products. There are also differences in the pyrograms of products of the same form derived from dissimilar monomers. The results obtained from P/GC generally support those derived from infrared or NMR measurements performed earlier.     

Determination of the carbon isotopic composition of whole/intact biological specimens using at-line direct thermal desorption to effect thermally assisted hydrolysis/methylation

In this paper, we discuss the use of a direct thermal desorption (DTD) interface as an alternative to Curie-point flash pyrolysis system as an inlet technique in gas chromatography-combustion isotope-ratio mass spectrometry (GC/C-IRMS) analysis of whole/intact phytoplankton and zooplankton specimens. The DTD in combination with a combipal auto-injector is programmed to perform the injection, evaporation of solvents, transport of capped programmed-temperature vaporizer (PTV) liners to the PTV injector and chemical derivatisation (thermally assisted hydrolysis/methylation; THM) such that a profile of a cellular fatty acids is obtained. Flow-cytometric sorted microalgae and handpicked zooplankton are used as samples with trimethylsulfonium hydroxide (TMSH) as methylating reagent. A major advantage of this novel approach over the Curie-point technique is the automation of the total procedure, which allows unattended analysis of large sample series. The profiles and delta(13)C carbon isotopic signatures of the fatty acid methyl esters (FAMEs) produced are very similar to those obtained using the Curie-point flash pyrolysis method. It is shown that algal samples must be kept no longer than 48 h in the DTD sample tray prior to the THM-analysis in order to maintain the integrity of their FAME profile.     

Thermal Degradation of Cotton Cellulose

The thermal degradation of cotton cellulose treated with chemical mixtures containing P and N was studied by thermal analysis, infrared spectroscopy, Char yield and limiting-oxygen-index (LOI). Our experiments demonstrated the following facts. The temperatures and activation energies of pyrolysis were lower for cotton cellulose treated with flame retardants than those for untreated samples and the values of Char yield and LOI were greater for treated cotton than those for untreated one. This revised version was published online in August 2006 with corrections to the Cover Date.     

生物质组分及温度对闪速热解挥发分的影响

生物质是一种可再生、污染小的自然资源，它可以直接燃烧产生热能，也可以转化为气体、液体燃料或化工原料。生物质热转化技术近年来受到国内外学者的广泛重视。而热转化过程中，热解是第一步，与生物质组分、热解温度、滞留时间等因素有关。热重仪（TGA）是一种研究热解机理常用的方法，它适用于慢速程序升温的热解研究。研究发现，热解条件及生物质种类对反应表观活化能与表观频率因子等动力学参数有很大影响。层流炉闪速加热设备，已经用于煤的热解研究。本文利用自己设计的以热等离子体为热源的层流炉系统，对椰子壳、棉花秆和稻壳粉末进行了闪速热解实验研究及模型理论分析，探讨了生物质化学组分、热解温度和滞留时间对挥发分的影响，为生物质闪速热解提供了一定的基础数据。     

水热处理对白石湖煤热解过程中钠钙迁移行为的影响

采用高压釜对富镜质组白石湖煤进行了水热处理,通过傅里叶红外光谱(FT-IR)分峰拟合方法分析了煤中含氧官能团变化。在固定床中开展分离废液和未分离废液水热处理煤样的热解实验,利用原子吸收分光光度计(AAS)测定了热解产物中钠钙含量。结果表明,白石湖煤经水热处理后水分、挥发分、氧含量以及Cl、Na和Ca等无机元素含量明显降低。水热处理过程中芳香醚水解和羧酸盐发生离子交换反应使得氢含量和H/C原子比增加,促进固定床热解焦油产率升高。300℃下水热处理脱除了部分有机形式Ca后随水废液被分离;废液中钠钙等无机元素的催化作用导致未分离废液较分离废液的样品具有更高热解气产率和更低焦油产率。白石湖原煤及其水热处理样品热解产物中Na含量和分布由高到低顺序均为:热解焦热解水焦油热解气,Ca含量和分布顺序为:热解焦焦油热解水热解气。水热处理温度越高,热解过程钠和钙释放率越低,释放的Na主要进入热解水,其次焦油;而释放的Ca则主要分布于焦油中,其次热解水。     

Pyrolysis of polypropylene: I. Identification of compounds and degradation reactions

Pyrolysis of two polypropylene samples (degrees of isotacticity 0.50 and 0.85) has been carried out by flash pyrolysis and distillation pyrolysis. The analytical coupling of flash pyrolysis, gas chromatography and mass spectrometry allowed the analysis of the degradation products and their evolution with temperature between 500 and 900°C to be followed under different experimental conditions.The mechanism of polypropylene degradation is compared with the radical mechanism of polystyrene degradation.The depolymerization reaction leading to the production of monomer (25%) is not the most important degradation reaction. The transfer reactions predominate and generate the following products: 2,4-dimethyl-1-heptene (27–32%), pentane (ca. 8%), 2,4,6,8-tetramethyl-1-hendecene (7–18%) and 2,4,6-trimethyl-1-nonene (4–10%).     

Improvement of hydrothermal stability and chrome uptake of leather: Amino-terminated hyper-branched polymer as high exhausted tanning auxiliary

Carboxyl-terminated hyper-branched polyester is extensively used as high exhaustion chrome tanning auxiliary owing to its strong coordination ability with trivalent chrome. Owing to lower electronegativity of N than O, the coordination ability with trivalent chrome for hyper-branched polyamide is stronger than polyester. Herein, in this paper, an amino-terminated hyper-branched polyamide (HBPN) is synthesized and used as high exhaustion chrome in tanning of pickling pigskin (HBPN–Cr). The effects of utilization of HBPN in denaturation temperature, shrinkage temperature, chrome uptake, and microstructure structure of wet-blue leather are studied. Moreover, the anti-oxidation stability of wet-blue leather is preliminary studied by heat treatment. The results show that incorporation of 1% HBPN in pickling process can significantly improve chrome uptake to 83.32%. The hydrothermal stability of wet-blue leather is improved due to the formation of higher crosslinking degree of collagen fibers. In addition, for the wet-blue leather without unsaturated fatliquoring agent, through heat treatment, hexavalent chrome does not appear after 24 ​h heat treatment. On the contrary, the chrome complex changes from hydroxyl copolymerization to more stable oxygen copolymerization or chrome oxide for C–Cr and HBPN-Cr tanned leather, respectively. These results will build a data support for the further study of hyper-branched polymer chrome tanning auxiliaries.     

Characteristics of kenaf fibre/epoxy composites subjected to thermal degradation

Kenaf fibres are receiving much attention in the natural fibre composite industry due to its potential as polymer reinforcements. However, like all natural fibres, kenaf fibres have lower thermal resistance as compared to synthetic fibres. In this current work, the characteristics of kenaf fibre/epoxy composites, both treated and untreated using alkalization process, exposed to high temperature were studied. Thermogravimetric analysis (TGA) was used to study the thermal decomposition behaviour of treated and untreated kenaf/epoxy composites as well as their components, kenaf fibre and neat epoxy from room temperature up to 600 °C. The weight loss and physical changes of these samples were observed through furnace pyrolysis. Surface morphology of the composites after degradation was observed using scanning electron microscopy (SEM). The results from the TGA showed that the addition of kenaf fibres into the epoxy slightly improves both the charring and thermal stability of the samples. However, it was observed that alkalization causes reduction in these behaviours for the kenaf/epoxy composite. Generally, increased exposure time causes higher weight loss of the composites only up to 150 °C. At higher temperature, duration of exposure has little influence on the weight loss. Fibre-matrix debondings were observed on degraded samples implying mechanical degradation of the composites had occurred.     

Study of the pyrolysis of municipal solid waste for the production of valuable products

To obtain information on the potential of thermal conversion (pyrolysis) of municipal solid waste (MSW), a thermogravimetric study (TGA) is performed in a stream of nitrogen. Based on TGA results, pyrolysis experiments are carried out in a semi-batch reactor under inert nitrogen atmosphere. Slow pyrolysis is performed up to 550 °C (heating rate of 4 °C/min). Fast pyrolysis is performed at 450, 480, 510 and 550 °C and different input transfer rates (12 or 24 g material/min). The pyrolysis products are studied on composition and yield/distribution and investigated for their use as valuable product.The liquid obtained by slow pyrolysis separates spontaneously in a water rich product and an oily product. For all fast pyrolysis conditions, a viscous, brown oil which contains a poly(ethylene-co-propylene) wax is obtained. Composition analyses by GC/MS of the oil products (slow/fast pyrolysis) show that aliphatic hydrocarbons are the major compounds. The pyrolysis oils have high calorific value (between 35 and 44 MJ/kg), low wt% of water (around 6 wt%) and a low O/C value (between 0.2 and 0.3). The presence of waxy material is probably due to incomplete breakdown of poly(ethylene-co-propylene) present in MSW under study. The optimal pyrolysis conditions, regarding to oil yield, fuel properties, and wax yield is fast pyrolysis at 510 °C with 24 g material/min input transfer rate. The fast pyrolysis gases contain mainly hydrocarbons and have an averaged LHV around 20 MJ/Nm³. ICP-AES analyses of pyrolysis products reveal that almost none of the metals present in MSW are distributed within the liquid fractions.     

Effects of nano nickel powders addition on flash pyrolysis of poly(ethylene glycol)

Pure PEG and the mixture of PEG and nano nickel powders (PEG/n-Ni) were pyrolyzed at 500 °C for 5 min in N₂ atmosphere. GC/MS and FTIR were employed to detect the volatile products. Some important regularity in the mass spectra of the PEG pyrolysis products was discovered, and 11 series of PEG pyrolysis products were identified. The experimental results show that the nano Ni powders evidently change the relative contents of each products series. The statistical results of the ratio of C-O cleavage to C-C cleavage, as well as the ratio of hydrogenation to dehydrogenation, indicate that nano Ni powders have remarkable effects on the bonds cleavage and free radicals annihilation. The process of hydrogenolysis and hydrogenation were propounded to explain the effects of nano Ni addition on PEG flash pyrolysis.     

Tannin fingerprinting in vegetable tanned leather by solid state NMR spectroscopy and comparison with leathers tanned by other processes

Solid state 13C-NMR spectra of pure tannin powders from four different sources--mimosa, quebracho, chestnut and tara--are readily distinguishable from each other, both in pure commercial powder form, and in leather which they have been used to tan. Groups of signals indicative of the source, and type (condensed vs. hydrolyzable) of tannin used in the manufacture are well resolved in the spectra of the finished leathers. These fingerprints are compared with those arising from leathers tanned with other common tanning agents. Paramagnetic chromium (III) tanning causes widespread but selective disappearance of signals from the spectrum of leather collagen, including resonances from acidic aspartyl and glutamyl residues, likely bound to Cr (III) structures. Aluminium (III) and glutaraldehyde tanning both cause considerable leather collagen signal sharpening suggesting some increase in molecular structural ordering. The 2?Al-NMR signal from the former material is consistent with an octahedral coordination by oxygen ligands. Solid state NMR thus provides easily recognisable reagent specific spectral fingerprints of the products of vegetable and some other common tanning processes. Because spectra are related to molecular properties, NMR is potentially a powerful tool in leather process enhancement and quality or provenance assurance.     

Kinetics modeling & comparative examine on thermal degradation of alkali treated Crotalaria juncea fiber using model fitting method

This study aims at investigating pyrolysis kinetics of untreated and alkali-treated Crotalaria juncea (sunnhemp) fiber by widely used model fitting Coats-Redfern method using TGA data. A kinetics study of thermal decomposition has been done for both untreated and treated fiber with the help of TGA using a single heating rate of 10 °C/min. This analysis shows that treated sunnhemp fibers have variable activation energy based on the different models chosen. The estimated activation energy is in the range of 30.0–76.6 kJ mol^?1 for the untreated sample & for the treated sample it is in the range of 34.58–67.12 kJ mol^?1. Here the two phases have been selected as per temperature ranges in which inherent component decomposes during pyrolysis. In each phase, kinetics and thermodynamic parameters (ΔS, ΔH & ΔG) are also estimated. FTIR study of both samples confirms the concentration change of elements present in fiber due to the chemical treatment performed.     

Thermal analysis/mass spectrometry using soft photo-ionisation for the investigation of biomass and mineral oils

The combined analytical methods of thermal analysis and mass spectrometry have been applied in form of a newly developed prototype of a thermogravimetry — single photon ionisation time-of-flight mass spectrometer coupling (TG-SPI-TOFMS) to investigate the molecular patterns of evolved gases from several biomass samples as well as a crude oil sample. Single photon ionization (SPI) was conducted by means of a novel electron beam pumped argon excimer lamp (EBEL) as photon source. With SPI-TOFMS various lignin decomposition products such as guaiacol, syringol and coniferyl alcohol could be monitored. Furthermore, SPI allows the detection of aliphatic hydrocarbons, mainly alkenes, carbonylic compounds such as acetone, and furan derivatives such as furfuryl alcohol and hydroxymethylfurfural. More alkaline biomass such as coarse colza meal show intense signals from nitrogen containing substances such as (iso-)propylamine and pyrrole. Thermal degradation of crude oil takes place in two steps, evaporation of volatile components and pyrolysis of larger molecular structures at higher temperatures. Due to the soft ionisation, homologue rows of alkanes and alkenes could be detected on basis of their molecular ions. The obtained information from the thermal analysis/photo ionisation mass spectrometry experiments can be drawn on in comparison to the investigation of the primary products from flash pyrolysis of biomass for production of biofuels and chemicals.     

Determination of concentrations of chromium and other elements in soil and plant samples from leather tanning area by Instrumental Neutron Activation Analysis

Chromium, one of the toxic elements, along with other elements has been determined in samples of soil and plant (leaves and seeds) from Jajmau Area, Kanpur district, India, which is irrigated with effluent waste water from leather tanning industries. Soil and plant samples were collected from these areas and analyzed by Instrumental Neutron Activation Analysis (INAA) using high flux reactor neutrons and high resolution gamma-ray spectrometry. Concentrations of fifteen elements in soil and five elements in plant samples were determined by relative method. Chromium concentrations were found to be in range of 45–3,900 mg kg^?1in soil samples and 14–83 mg kg^?1 in plant samples. This study showed that Cr is present in significant amounts, in the soil as well as in the plant samples, near to the leather tanning area. As a part of quality control work, IAEA reference material (RM) SL-3 and NIST standard reference material (SRM) 1645 were analyzed and the quality of the results has been evaluated by calculating % deviations from recommended/literature/certified values.     

The effect of metal ions on thermal oxidative degradation of cotton cellulose ammonium phosphate

The thermal oxidative degradation of cellulose, and of cellulose ammonium phosphate and its metal complexes products were studied by thermal analysis, infrared spectroscopy and elemental analysis. The temperature of decomposition was lower for metal complexes of cellulose ammonium phosphate than those samples untreated by metal ions and the values of char yield were greater for treated cellulose than those untreated. This indicates the metal ions can catalyze the reaction of degradation and form more char. This revised version was published online in August 2006 with corrections to the Cover Date.     

三硝基均苯三酚金属(Li,Na, K,Mg)化合物的快速热分解

利用温度快速跃升傅立叶变换红外(T-jump/FTIR)原位分析技术对三硝基均苯三酚(TNPG, 2,4,6-三硝基-1,3,5-苯三酚)的锂、钠、钾、镁金属盐的快速热分解反应过程进行了系统研究. 确定了三硝基均苯三酚系列化合物快速热分解过程产生的可挥发金属化合物的类型, 得到了快速热分解过程主要红外活性气体产物的种类、分布及浓度随时间的变化关系曲线, 提出了其快速热分解方程式. 利用计算机模拟方法, 采用REAL程序对三硝基均苯三酚系列化合物的燃烧性能(燃烧产物和燃烧温度等参数)进行了计算, 与T-jump/FTIR分析技术得到的实验结果进行比较分析和讨论.