Mechanism of Chrome-free Tanning with Tetra-hydroxymethyl Phosphonium Chloride

Tetra-hydroxymethyl phosphonium chloride （THPC） has been considered as an important chrome-free tanning agent. To understand the THPC tanning mechanism, the structure, charge distribution, activity and tanning ability of each phosphorous compound in THPC tanning system were studied, by ^31p NMR, FT-IR spectroscopy, differential scanning calorimetry （DSC） and computational chemistry method, etc. When pH raised to 6.0, the decomposition of THPC would take place, which results in a production of free formaldehyde, tri-hydroxymethyl phosphonium （TrHP） and tri-hydroxymethyl phosphine oxide （TrHPO）. At pH 9.0, THPC will be converted completely to TrHP and most TrHP is further oxidized into TrHPO. It is possible that, in reaction of phosphorous compounds and collagens, both P-C and C-O bonds would break simultaneously or individually. From molecular charge distribution and bond polar properties, it is deduced that, if P-C bonds break, the activity is in order of TrHPO 〉 THPC 〉 TrHE whereas if C--O bonds break, the order is TrHP 〉 THPC 〉 TrHPO. It is more possible that P--C bonds will break in reaction with collagen, and TrHPO may be more active in the THPC tanning system. The results of tanning and DSC also prove the above conclusion. Furthermore, the fact that the shrinkage temperature of THPC tanned leather was below 70℃ when basified to pH 5.0 or lower suggests that the hydroxymethyl groups of THPC and TrHP are less possible to combine directly with amino groups of collagen.

Investigation of Formation Process of the Chrome-free Passivation Film of Electrodeposited Zinc

The feasibility was investigated to substitute chrome-free passivation treatment of electrodeposited zinc in a titanium bath for chromate passivation treatment. The formation mechanism of the chrome-free passivation film was further analyzed. The surface mor- phologies and the elemental compositions of the treated samples with varied immersion times were observed by scanning electron mi- croscopy （SEM） and determined by energy dispersion spectrometry （EDS）, respectively. The electrode potential of the sample surface was recorded in the film formation process. The changes of the electrode potential are in accordance with that of SEM and EDS of the sample surface. The results of X-ray photoelectron spectroscopy （XPS） show the chrome-free passivation film composed ofZnO, SiO2, TiO2, Zn4Si207（OH）2, and SrF2. The anode zinc dissolution and the local pH value increase due to the cathode hydrogen ion reduction process result in the formation of the chrome-free passivation film. The macro-images of the chrome-free passivation films formed on electrodeposited zinc show that the color of the film changes from blue to iridescence with the increase of the immersion times.

Development and Application of Chrome-free Refractory Materials for RH Degasser

The research progress and industrial application of chrome-free refractories for RH degasser were introduced in the paper.It is proved that unburned magnesia-spinel refractories used for RH throat and snorkel in Baosteel have longer service life compared with traditional direct bonded fused magnesia-chrome materials.The new developed chrome-free unburned magnesia-spinel composite can fully meet the present demand for RH operation and can be applied extensively for RH processing.At present,instead of chrome-containing materials,chrome-free refractories have been applied widely for RH in Baosteel.Super low carbon MgO-C material with high mechanical properties at mild and high temperatures can be an alternative chrome-free material for RH.

ELECTROPLATED Zn-Ni-SiO_(2) COMPOSITE COATINGS TREATED WITH A SILANE COUPLING AGENT TO REPLACE CHROMATING

The fixing of a silane coupling agent to Zn-Ni-silica(SiO_(2))composite coatings was studied for the purpose of developing a coating process as an alternative to chromating.The corrosion resistance of Zn-Ni-silica composite coatings was rem arkably improved by the silica nanoparticles in the composite,which were disper sed in the surface of this film.The silane coupling agent formed chemical bonds with the inorganic silica particles during the silane coupling treatment on the se composite coatings.The treatment suppressed the formation of white corrosion products to the same extent as chromating,as measured in salt spray tests.It is concluded that treating Zn-Ni-silica composite coatings with silane coupling agents is a viable alternative technique to chromating.

A Novel Approach to Clean Tanning Technology

Traditional chrome tanning technology is still widely used today. In this technology, chrome shaving as well as chrome contained effluent in tanning and retanning processes is a big issue in the industry. Wet white tanning technology has been gaining in importance in recent years, but in general, the comprehensive performance of chrome-free tanned leather is not comparable with that of chrome tanned leather. In the present work, chrome-free tanning and chrome tanning are combined in a reversed procedure, which produces leather with chrome tanned leather quality without chrome tanned leather waste problems. In this procedure, a special amphoteric organic compound, no pickle, no salt chrome-free tanning agent TWT was used to tan delimed hides （no pickle） making wet white with shrinking temperature at 80-85 ~C. Then, new method called reversed tanning further process the wet white into chrome-tanned crust. In this reversed method, retanning, fatliquoring and coloring processes were carried out before chrome tanning. This technology eliminates chrome waste issue in tanning, shaving, post tanning processes. The chrome contained effluent is only concentrated in the last chrome tanning process. The leather made with this technology has complete conventional chrome-tanned leather quality. In this way, chrome leather quality without chrome waste problems was achieved. So, it is a new clean tanning technology.

Corrosion resistance evaluation of highly dispersed MgO–MgAl2O4–ZrO2 composite and analysis of its corrosion mechanism: A chromium-free refractory for RH refining kilns

The corrosion resistance behavior of a highly dispersed MgO-MgAl2O4-ZrO2 composite refractory material is examined by testing with high-basicity and low-basicity RH(Ruhrstahl-Hereaeus)slags.The composite material exhibits greater resistance to the RH slags than the traditional MgO-Cr2O3 composite,MgO-ZrO2 composite,and MgO-MgAl2O4-ZrO2 composite.On the basis of the microstructural analysis and mechanisms calculations,the corrosion resistance behavior of the MgO-MgAl2O4-ZrO2 composite is attributable to its highly dispersed structure,which helps protect the high activity of ZrO2.When in contact with the slag,ZrO2 reacts with CaO to form the stable phase CaZrO3,which protects MgAl2O4 against corrosion,thereby enhancing the corrosion resistance of the composite.

A chrome-free combination tanning strategy: based on silicic acid and plant tannin

Silicic acid,commonly derived from cheap and easily available sodium silicate,has recently received great attention for application in leather industry to produce ecological leather with a cleaner approach.However,leather tanned with silicic acid alone is poor in storage stability,which limits its practical application in leather production.In this work,a new environment-friendly combination tannage based on silicic acid and plant tannin was developed to address this issue along with improving the comprehensive performances of leather.The obtained leather was characterized by scanning electron microscopy,Fourier transform infrared spectroscopy,X-ray photoelectron spectroscopy and so on.The results showed that compared with leather tanned with silicic acid alone,the leather tanned with this combination method possessed improved thermal stability,enhanced mechanical properties,acceptable softness,appropriate hydrophilicity,and especially enhanced storage stability.More importantly,the combination tanned leather with 1:1 of the mass ratio of silicic acid to vegetable tannin(composed of valonea extract and mimosa extract with the same weight)had more prominent comprehensive performances.In addition,the results demonstrated that hydrogen bonding played an important role in the combination tanning process.Furthermore,the hydrogen bonds generated between phenolic hydroxyl groups of polyphenols with silicon hydroxyl groups of silicic acid molecules inhibited the excessive condensation of Si-OH groups between themselves.Subsequently,the assessment of environmental impact revealed the value of BOD 5/COD of the wastewater produced in this combination tanning process is more than 0.3,indicating the chrome-free combination tannage based on silicic acid and plant tannin was an environment-friendly tanning technology.These findings therefore indicated that a new chrome-free tanning method with silicon and biomass materials as main tanning agents has potential practical application prospect in leather production.

Progress in Research on Vanadate-Based Coatings on Corrosion Resistance

Vanadate, usually used as the corrosion resistant inhibitor for the paint systems, is one of the substances that have been proposed as alternative to toxic chromate for the corrosion protection. In this paper, the possibility of vanadate passivating from its chemical properties was introduced firstly. Then, the progress and examples in research on vanadate conversion coatings on the corrosion resistance were summarized. And the substrates discussed here contained aluminum alloys, magnesium alloys and so on. Finally, the research tendency of vanadate-based coatings was discussed.

Self-driven directional dehydration enabled eco-friendly manufacture of chrome-free leather

Manufacture of eco-friendly chrome-free leather is of great significance for realizing sustainable development of leather industry.Conventional tanning theory believes that it is impossible to convert raw hide to leather without the utilization of cross-linking agent(e.g.,chrome salts)among collagen fibers in raw hide.Here,we developed a brand-new leather manufacture strategy that relied on the composite dehydration media enabled self-driven directional dehydration mechanism to accomplish chrome-free leather manufacture for the first time,rather than followed the classic cross-linking mechanism that has been obeyed for more than one century in leather industry.We demonstrated that the essence of leather making is to regulate the water content in raw hide rather than to form cross-linkage among collagen fibers.The composite dehydration media comprised of anhydrous ethanol and molecular sieves(3A activated zeolite powder)successfully guaranteed continuous self-driven directional dehydration of raw hide by establishing stable water concentration gradient between raw hide and ethanol,which significantly increased the dispersity of collagen fibers in raw hide(with the water content reduced from 56.07%to 5.20%),thus obtaining chrome-free leather that is more ecological than chrome-tanned leather due to the elimination of any tanning agent.The as-prepared chrome-free leather exhibited outstanding tear force(174.86 N),tensile strength(24.56 N mm−2),elongation at break(53.28%)and dry-thermal stability,superior to chrome-tanned leather.Notably,the used compos-ite dehydration media was recyclable for chrome-free leather manufacture,therefore facilitating an environmentally benign leather manufacture process.Our investigations are expected to open up a new conceptual leather making strategy that is applicable for realizing substantial manufacture of eco-friendly leather.

Research on Refractories Technology to Meet the Demands of Steel-making Process

Based on the refractories research of Baosteel, the demands for refractories from the developing steel-making technology as high security, high efficiency, energy saving and environment .friendly are introduced.

Interaction between retanning agents and wet white tanned by a novel bimetal complex tanning agent

A promising and practical chrome-free tanning system has been developed based on a novel Al–Zr bimetal complex tanning agent.However,to achieve satisfactory resultant leather,the retanning process that is compatible with this emerging tannage needs to be investigated systematically.This paper aims to explore the interaction between the bimetal complex tanned wet white and retanning agents.The isoelectric point(pI)of wet white was 7.2,which was nearly the same as wet blue.The electropositivity of wet white was even higher than that of wet blue during post-tanning processes,resulting in higher uptake rate of retanning agents.The distribution of various retanning agents in wet white was analyzed by pI measurement of layered leather and fluorescent tracing technique.The retanning agents were unevenly distributed throughout the cross-section,which might be an important restriction factor in obtaining satisfactory organoleptic properties of the crust leather.This fact is mainly due to the strong electrostatic interaction between anionic retanning agents and wet white.Applying a high dosage of multiple retanning agents in a proper sequence of addition benefited the full penetration of retanning agents in leather matrix and thus improved the organoleptic properties of crust leather.This work provides guidance for optimizing retanning process of the wet white leather.

Process Optimization for Cerium Oxide Based Conversion Coating of AZ91D Magnesium Alloy at Room Temperature

The Ce2SO4/H2O2 containing solution is used to prepare a chrome-free cerium oxide based chemical conversion coating on AZ91D magnesium alloy at room temperature,and an orthogonal experiment was carried out to optimize the treating process.The effect of preparing parameters on the coating growth and the corrosion resistance were studied.It was found that H2O2 is the dominant influence factor on the coating weight gain in the orthogonal experiment,with Ce(SO4)2 coming next and immersion time having the least impact,while the most dominant influence factor on the corrosion resistance is Ce(SO4)2,with H2O2 coming next and immersion time having the least impact.The coating has the best corrosion resistance,treated in the solution of 10 g/l Ce(SO4)2 and 12 ml/l H2O2 for 4 min.SEM was adopted to study the micro-morphology of the conversion coating on magnesium alloy surface The prolonged immersion time duration or the increased concentration of Ce(SO4)2 and H2O2 will increase the coating thickness,but tiny cracks appears resulted from the fast coating deposition.

Extraction of a novel tanning agent from indigenous plant bark and its application in leather processing

The use of vegetable tanning materials in leather processing has drawn attention as an alternative to basic chromium sulphate for its natural abundance and environmental aspects.In this work,an attempt has been made to extract vegetable tannins from Xylocarpus granatum bark using different solvents(e.g.,water,methanol,ethanol,and chloroform)and compare with conventional vegetable tanning agents such as mimosa and quebracho.The highest extraction efficiency was observed 31.22%by methanol.The presence of tannin content and polyphenolic compounds,e.g.(-)epicatechin(503 mg/100 g dry extract),catechin hydrate(218 mg/100 g dry extract),catechol(29 mg/100 g dry extract)were ensured by UV-Vis,FT-IR spectroscopy and HPLC.Again,condensed tannins,moisture content,and pH of the methanol extracted tannin were found 47.80%,5.82%,and 3.97 respectively.The leather tanned by Xylocarpus granatum tannin showed a shrinkage temperature of 86.34±1.52℃.Other properties such as tensile strength,tear strength,grain cracking load,and distention at grain cracking were comparable to conventional vegetable-tanned leather.The cross-sectional morphology of the tanned leathers was also characterized by scanning electron microscopy(SEM)which revealed a compact structure of the leather fibers.In light of the findings from the study,X.granatum bark tannin could be a well alternative to chromium and a new source of vegetable tannin for the leather industry.

Extraction of a novel tanning agent from indigenous plant bark and its application in leather processing

The use of vegetable tanning materials in leather processing has drawn attention as an alternative to basic chromium sulphate for its natural abundance and environmental aspects. In this work, an attempt has been made to extract veg-etable tannins from Xylocarpus granatum bark using different solvents (e.g., water, methanol, ethanol, and chloroform) and compare with conventional vegetable tanning agents such as mimosa and quebracho. The highest extraction efficiency was observed 31.22% by methanol. The presence of tannin content and polyphenolic compounds, e.g. (-)epicatechin (503 mg/100 g dry extract), catechin hydrate (218 mg/100 g dry extract), catechol (29 mg/100 g dry extract) were ensured by UV-Vis, FT-IR spectroscopy and HPLC. Again, condensed tannins, moisture content, and pH of the methanol extracted tannin were found 47.80%, 5.82%, and 3.97 respectively. The leather tanned by Xylocar-pus granatum tannin showed a shrinkage temperature of 86.34 ± 1.52 °C. Other properties such as tensile strength, tear strength, grain cracking load, and distention at grain cracking were comparable to conventional vegetable- tanned leather. The cross-sectional morphology of the tanned leathers was also characterized by scanning electron microscopy (SEM) which revealed a compact structure of the leather fibers. In light of the findings from the study, X. granatum bark tannin could be a well alternative to chromium and a new source of vegetable tannin for the leather industry.