NUCLEATION AND GROWTH ACTIVATION ENERGIES DURING CRYSTALLIZATION OF AMORPHOUS ALLOYS (Ⅱ)——RELATIONSHIP BETWEEN MICROSTFUCTURE OF AMORPHOUS STATE AND TEMPERATURE

By using the new method for determination of activation energies for nucleation andgrowth (E_n & E_g) developed in Part Ⅰ of this work, the E_n and E_g of some pre--annealedamorphous Ni--P alloys, as well as those of the as--quenched Ni--P glass within differenttemperature ranges are measured and studied. The results show that the values of E_n and E_gare closely related to the microstructure of amorphous alloys and the annealing temperature.The higher the ordering in the amorphous alloys, the smaller the values of E_n and E_g; thehigher the annealing temperature, the greater the E_n and E_g values. By means of the newlydeveloped crystallization micromechanism, such an experimental phenomenon which is diffi-cult to understand from the classical crystallization mechanism is reasonably explained.     

电沉积法制备Fe与La、Ce的非晶态合金及其晶化动力学研究

Fe-La, Fe-Ce, Fe-La-P, Fe-Ce-P and Fe-P alloys were obtained from aqueous solutions by using optimized electroplaing solutions and process conditions. The experimental results show that these alloys (Fe-La-P, Fe-Ce-P and Fe-P) have amorphous structure. The crystallization activation energy and kinetics equation of three kinds amorphous coatings have been determined by DSC method. The results indicated that the crystallization activation energy of Fe-P, Fe-La-P, Fe-Ce-P amorphous coatings are 175.2, 370.1, 434.6kJ·mol^-1 respectively. The crystallization mechamism of three kinds amorphous alloys may be expressed by Avrami-Erofeev equation (n=1), the kinetics equation is dα/dT=A/Φ e^-E/RT(1-α).     

Chemical preparation and investigation of Fe-P-B ultrafine amorphous alloy particles

A series of Fe-P-B ultrafine amorphous alloy particles has been prepared by the chemical reduction method The composition and size of the particles have been effectively adjusted.Mossbauer spectroscopy in addition to sonic other techniques has been used to investigate the reaction process,the factors that influence the preparation,the crystallization of the particles,and the interactions between the components within them.The results indicate that the co-deposition of iron,phosphorus and boron atoms in the solution at room temperature forms Fe-P-B amorphous alloy particles,and a preferential bonding of Fe-P bond to Fe-B one exists in the particles.     

Characterization and Catalytic Properties of a Rapidly Quenched Ni-RE-P-AL Catalyst

IntroductionAmorphous.alloy has been found to have superior catalytic properties["']. However, asan applied catalyst, its small surface area and low thermal stability during the catalytic processare the encountered problems usually.In the previous study, we found that addition of a small amount of rare earth element effectively stabilized the amorphous phase in a Ni--P alloyL'~'j, and the surface area of the amorphous Ni--RE--P alloy could be greatly enlarged by introducing Al into the Ni-…     

WAXD STUDY OF POLYMORPHOUS ISOTACTICPOLYPROPYLENE BY COMPUTER PEAK-RESOLUTION METHOD

Polymorphous i-PP containing a and βphases were studied by WAXD and computer peak-resolution method (CPRM). The asymmetric Gaussian-Cauchy functions (a-GC) were adoptedto fit the profiles of both amorphous and crystalline peaks. For the crystalline peaks, the fitting resultsof a-GC are better than the symmetric-GC; for the amorphous peaks, they are better than polynomialand exponential functions, etc. Using the retarded least-square procedure (RLSP) on microcom-puter the results of peak-resolution are rather satisfatory. For the polymorphous samples containingαand βphases, the relations between phase-state, crystallinity, crystalline size, the ratio of α,βrelativecontent and the crystallization temperature T_c were studied by CPRM. The ratio of α,βrelativecontents obtained by CPRM and Turner-Jones eq. have been carefully compared. There are manyimprovements in this work. A simple estimation method of WAXD peak areas, both for amorphousand crystalline peaki, is suggested.     

Investigation on the gelation behavior of biodegradable poly(butylene succinate) during isothermal crystallization process

The early stage of polymer crystallization may be viewed as physical gelation process,i.e.,the phase transition of polymer from liquid to solid.Determination of the gel point is of significance in polymer processing.In this work,the gelation behavior of poly(butylene succinate)(PBS) at different temperatures has been investigated by rheological method.It was found that during the isothermal crystallization process of PBS,both the storage modulus(G′) and the loss modulus(G″) increase with time,and the rheological response of the system varies from viscous-dominated(G′G″),meaning the phase transition from liquid to solid.The physical gel point was determined by the intersection point of loss tangent curves measured under different frequencies.The gel time(t_c) for PBS was found to increase with increasing crystallization temperature.The relative crystallinity of PBS at the gel point is very low(2.5%-8.5%) and increases with increasing the crystallization temperature.The low crystallinity of PBS at the gel point suggests that only a few junctions are necessary to form a spanning network,indicating that the network is"loosely"connected,in another word,the critical gel is soft.Due to the elevated crystallinity at gel point under higher crystallization temperature,the gel strength S_g increases, while the relaxation exponent n decreases with increasing the crystallization temperature.These experimental results suggest that rheological method is an effective tool for verifying the gel point of biodegradable semi-crystalline polymers.     

The change in thickness of the solidified liquid layer rather than the immobilized mass determines the frequency response of a quartz crystal microbalance

The "solidified liquid layer" model has been examined using a quartz crystal microbalance(QCM) with a polymeric matrix.The model is shown to give a reasonable explanation for the following experimental observations:(i) The opposite response of the QCM and surface plasmon resonance(SPR) for the activation process;(ii) the marked difference in the responses for IgG/anti-IgG interaction between QCM and SPR.Theoretical analysis and experimental results indicated that QCM is sensitive to the thickness change of the "solidified liquid layer" but not the mass of captured biomolecules(i.e.,the immobilized mass),implying caution must be taken in interpreting QCM results.     

Theoretical Study on the Catalytic Activity and Sulfur Resistibility of Amorphous Alloy Ni-B-P

In the present paper,one hundred cluster models NinBP (n=1～6) have been designed and studied by density functional theory (DFT) to get an insight into the local structure,catalytic properties and sulfur resistibility of amorphous alloy Ni-B-P. The configurations in triplet state are found more stable than those in the singlet state. It is found that as the content of Ni in the clusters increases,the value of Fermi level in clusters fluctuated,which shows that the content of Ni can influence the Fermi level to a certain extent. Based on the Fermi level and DOS,we consider the activity of catalyst in hydrogenation reaction is the best in cluster Ni3BP. On the basis of the charge of clusters NinBP (n=1～6),we conclude the amorphous alloy Ni-B-P with high Ni content has better sulfur resistibility and the best hydrogenation activity,strong sulfur resistibility appears in clusters Ni3BP,and the amorphous alloy Ni60B20P20 with similar proportion is expected to prepare in the future.     

拉伸热历史对取向聚对苯二甲酸乙二酯膜在热处理过程中收缩和伸长的影响

The effects of drawing temperature and draw ratio on the contraction and extension of oriented amorphous PET film during thermal treatment has been studied. It has been shown that considerable thermal contraction of the oriented PET film before crystallization is due to relaxation of molecular chains in global sense while the spontaneous extension is related to crystallization of the oriented PET film. The maximum amount of contraction of the oriented PET film during thermal treatment increased with increasing λfor λ>2.3,owing to faster crystallization rate of PET film in highly oriented state. The maximum extension exibits similar behavior as that of maximum contraction with increasing λ and showed a peak at λ≌ 3.3,which isalmost the same draw ratio above which the densityof PET film began to increase during drawing.     

TRANSAMIDATION IN THE in situ BLENDING OF POLYAMIDE 1212 WITH POLYAMIDE 6 THROUGH ANIONIC POLYMERIZATION OF CAPROLACTAM

20 wt% polyamide 12(PA1212)pellets were dissolved in molten caprolactam.The caprolactam was then catalyzed at 180℃and polymerized by means of anionic ring-opening polymerization to produce in situ blends of the resultant polyamide 6(PA6)and PA1212.Mechanical blends with same ingredient were prepared through melt blending on a twin-screw extruder.Scanning electron microscopy(SEM)observation revealed that contrary to the mechanical blends with small spherulites embedded in the matrix,no phase-separation existed in the in situ blends.The results of thermal analysis by differential scanning calorimetry(DSC)showed that single melting peak and crystallization peak existed for the in situ blends,while two melting and crystallization peaks appeared for the mechanical blends.The in situ blend film and the mixed blend film,both cast from a dilute formic acid solution with a concentration of 0.5 g/L,remained similar crystallization and melting behavior as above.It is proved by solution ~(13)C-NMR analysis that transamidation took place during the in situ blending,and it is suggested that the combination of temperature increasing and the basic surrounding derived from NaOH during polymerization resulted in the occurrence of transamidation.Furthermore,it is proposed that the interchange reaction between PA1212 and PA6 also resulted from the degradative reaction during the anionic polymerization.     

COS Activation by Zr~＋ in the Gas Phase：A Case of Two-state Reactivity Process

To elucidate the mechanisms of Zr + reacting with COS,both the quartet and doublet potential energy surfaces (PESs) for reactions of Zr + (4 F,2 D) with COS in the gas phase have been investigated in detail by means of density functional method (B3LYP).To obtain more accurate results,the coupled cluster single-point calculations (CCSD(T)) using B3LYP optimized geometries were performed.For the C-O bond activation,the calculated results indicate that both the quartet and doublet states proceed via an insertion-elimination mechanism.For the C-S bond activation,the quartet reaction has an insertion-elimination mechanism,but the doublet reaction is a direct abstraction of the sulfur atom by Zr +.The C-S bond activation is found to be energetically more favorable than the C-O bond activation.It is found that the reaction of the 4 F gound state of Zr + to yield ZrO + is spin-forbidden (Zr + (4 F) + COS (1 Σ) → ZrO + (2) + CS (1 Σ)) and the crossing points were approximately determined.All the results have been compared with the existing experimental and theoretical data.     

OPTICAL INTERFERENCE METHOD FOR THE STUDY OF MOISTURE SWELLING IN PET FILMS

A method for measuring moisture swelling of amorphous PET films by using Rayleigh interferometer is reported, Plots of the optical path of light transmission in the polymer vs. soaking time were obtained, and from the same curves, the dependence of time on the moisture swelling, saturated water absorption and diffusion coefficient of PET films were estimated. These results are in agreement with those obtained by weighing method. It is shown that optical interference method is a simple but sensitive method for the study of water absorption and swelling in transparent polymer films.     

The effects of ultrasound frequency and power on the activation energy in Si-KOH reaction system

The activation energy is the minimum amount of energy required to initiate a reaction. It is one of the important indexes for appraising a reaction. The chemical reaction rate is closely related to the value of activation energy, and reducing activation energy is propitious to promoting a chemical reaction. In the present paper, the relationship between the activation energy in Si-KOH reaction system and the ultrasound frequency and power has been discussed for the first time. The range of ultrasound frequency and power is 40-100kHz （interval by 20kHz） and 10-50W （interval by 10W）, respectively. The experimental clata indicate that the activation energy decreases with the increasing ultrasound power. Comparing with the activation energy without ultrasound irradiation, the results in our paper indicate that ultrasound irradiation could reduce the activation energy in Si-KOH reaction system and increase the reaction rate.     

Molecular dynamics study of the nucleation behavior and lamellar mergence in polyethylene globule crystallization

The site order parameter (SOP) has been adopted to analyze various orders of structure formation and distribution during the crystallization of a polyethylene globule simulated by molecular dynamics. The SOP not only identifies different orders among the structures but also different phases. The results showed that intermediate structures with medium order exist unevenly in the early stage of nucleation, which differs from traditional models. We found that the nucleation relies on crystallinity fluctuations with increasing amplitude, and a baby nucleus with different shape and increasing size suddenly appears in the fluctuations. Once its size is large enough, the baby nucleus becomes the nucleus. In the growth stage, a number of lamellar mergences were observed and their selective behaviors were related to the orientation differences between the lamellae to be merged. The SOP distribution of all atoms in the system during crystallization had two peaks: one for the amorphous phase and the other for the crystalline phase. The intermediate structures with medium orders are located between the two peaks as an order promotion pathway. The data show that the medium order structure fluctuates at the growth front and is not always available, and that the medium order structure existing at the front is not always good for development. It is possibly caused by chain entanglement. Structure fluctuation at the growth front enables the system showing thousands of the most probable configurations to approach the precursor. The growth front is thus active for a while and inactive at other times.     

A modified simplex method for multifactor optimization of selectivity in gas chromatography

A computer-assisted advanced simplex method is presented for the simultaneous optimization of multifactor ( stationary phase loading, carrier gas flow rate and column temperature ) for separation of ten compounds in gas chromatography. A three factors factorial design was used. The method was based on a special polynomial established from fifteen preliminary runs, using resolution as the selection criterion, with connection to a general simplex method. Excellent agreement is found between the predicted data and the experimental results, and most of experiments required in the general simplex method can be omitted.     

气相色谱法测定线虫中的脂肪酸含量

ematode is a small organism and the traditional purification method needs a lot of nematodes , but it is difficult for us to foster many nematodes.The fatty acids in nematode were esterified directly in our analytical method,so that,the error is reduced the and sensitivity is improved. The results showed that thisimproved analysis method could be used for rapid and satisfactory determination of the fatty acid change during storagr of this group of nematodes.     

Electronic factor in electron self-exchange reaction of hydrated redox ion pairs from thermodynamic data

An accurate scheme for determining the electronic factor of the electron self-exchange reaction in solution is presented in this paper. The used various activation parameters and slopes of potential energy surfaces are obtained in terms of an improved activation model and the accurate potential function determined from the vibrational spectroscopic and thermodynamic data. The coupling matrix elements are determined using numerical integral method over the perturbed double-zeta Slater-type state functions. Theoretical results of electronic factor in this work are found in close agreement with those extracted from experimental rate constant data and to be less than unity. Results indicate that outer-sphere electron transfer reactions in solution involving hydrated transition metal ions are nonadiabatic in nature.     

Computer-assisted optimization of temperature programming and flow rate in capillary gas chromatography

A computer-assisted method is presented for simultaneous optimization of three-factor of temperature programming (initial temperature, temperature rising rate and carrier gas flow rate) for the separation of eleven compounds in capillary gas chromatography. The optimization of the separation over the experimental region is based on a special polynomial from fifteen preliminary experiments using the resolution as the selection criterion. Computer scanning technique was used for optimum selection on three dimensions. Excellent agreement was found between the predicted data and the experimental results.     

Highly active electrocatalysis of hydrogen evolution reaction in alkaline medium by Ni–P alloy: A capacitance-activity relationship

Different weights of amorphous Ni–P alloy with same P contents were electrodeposited on nickel plate with same area used as cathode for hydrogen evolution reaction(HER). The amorphous Ni–P alloy coatings were characterized for their surface morphology and composition through Scanning electron microscopy(SEM) and Energy dispersive X-ray spectroscopy(EDS) techniques, X-ray photoelectron spectroscopy(XPS) and X-ray diffraction(XRD) analysis. The electrocatalytic activity for HER in alkaline medium is determined by linear scan voltammetry(LSV) and a relationship between HER activity and capacitance is established. The capacitance varies with the loading of the Ni–P on Ni plate but the activity for HER is directly proportional to the capacitance in alkaline and vice versa. 3#Ni–P/Ni containing 3.85 mg Ni–P alloy with highest capacitance performs the best catalytic activity. This work provides direct evidence to explore the capacitance influence on the electrocatalystic activity for the HER.