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 abili...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.展开更多
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 f...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.展开更多
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 Baost...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.展开更多
A significant enhancement in solar hydrogen generation efficiency has been achieved by inductive coupled etching （ICP） surface roughening treatment using nano-sized nickel mask. As much as 7 times improvement of pho...A significant enhancement in solar hydrogen generation efficiency has been achieved by inductive coupled etching （ICP） surface roughening treatment using nano-sized nickel mask. As much as 7 times improvement of photocurrent is demonstrated in comparison with a planar one fabricated from the same parent wafer. Under identical illumination conditions in HBr solution, the incident photon conversion efficiency （IPCE） shows an enhancement with a factor of 3, which even exceed 54% at 400 nm wavelength. We believe the enhancement is attributed to several facts including improvement in absorption, reacting area, carder localization and carrier lifetime.展开更多
Impingement heat transfer from the rib roughened surface within 2 dimensional arrays of circular jet has been experimentally investigated.This investigation is intended here to include the flow and the heat transfer c...Impingement heat transfer from the rib roughened surface within 2 dimensional arrays of circular jet has been experimentally investigated.This investigation is intended here to include the flow and the heat transfer characteristics of the jet impinging on the rib roughened surface with initial crossflow for simulating the impingement cooling midchord region of the gas turbine aerofoils in case where an initial crossflow is presented.The study covered the ranges of crossflow G_(c)/G_(j)=0~0.55 under the conditions of Re_(j)=8000~11000 and Z/d=1.5~3.0 for smooth and rib roughened surfaces.The test results show that the impingement heat transfer from the rib roughened surface is considerably affected by the initial crossflow rate.The existence of the initial crossflow will improve the efficiency of the impingement heat transfer from the rib roughened surface within arrays of circular jet compared with that from the smooth surface.展开更多
基金the National Basic Research Program (2007CB616909)Startup Foundation of Applied Chemistry of the Key Discipline of Zhejiang University of Technology and Zhejiang Provincial Science and Technology Plan (2006C21107)
文摘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.
文摘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.
文摘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.
基金supported by the Special Funds for Major State Basic Research Project of China(Grant Nos.2011CB301900,2012CB619304,and 2010CB327504)the Hi-tech Research Project of China(Grant No.2011AA03A103)+4 种基金the National Nature Science Foundation of China(Grant Nos.60990311,61274003,60936004,and 61176063)the Program for New Century Excellent Talents in University of China(Grant No.NCET-11-0229)the Natural Science Foundation of Jiangsu Province of China(Grant No.BK2011010)the Funds of Key Laboratory of China(Grant No.9140C140102120C14)the Research Funds from NJU-Yangzhou Institute of Opto-electronics of China
文摘A significant enhancement in solar hydrogen generation efficiency has been achieved by inductive coupled etching （ICP） surface roughening treatment using nano-sized nickel mask. As much as 7 times improvement of photocurrent is demonstrated in comparison with a planar one fabricated from the same parent wafer. Under identical illumination conditions in HBr solution, the incident photon conversion efficiency （IPCE） shows an enhancement with a factor of 3, which even exceed 54% at 400 nm wavelength. We believe the enhancement is attributed to several facts including improvement in absorption, reacting area, carder localization and carrier lifetime.
文摘Impingement heat transfer from the rib roughened surface within 2 dimensional arrays of circular jet has been experimentally investigated.This investigation is intended here to include the flow and the heat transfer characteristics of the jet impinging on the rib roughened surface with initial crossflow for simulating the impingement cooling midchord region of the gas turbine aerofoils in case where an initial crossflow is presented.The study covered the ranges of crossflow G_(c)/G_(j)=0~0.55 under the conditions of Re_(j)=8000~11000 and Z/d=1.5~3.0 for smooth and rib roughened surfaces.The test results show that the impingement heat transfer from the rib roughened surface is considerably affected by the initial crossflow rate.The existence of the initial crossflow will improve the efficiency of the impingement heat transfer from the rib roughened surface within arrays of circular jet compared with that from the smooth surface.
