Experimental Determination of Phase Equilibria
in the Co-Cr-Ni System
T.Omori,J.Sato,K.Shinagawa,I.Ohnuma,K.Oikawa,R.Kainuma,and K.Ishida (Submitted January14,2014;in revised form February7,2014;published online February26,2014)
The phase equilibria between the c(A1)and liquid phases and those between the c,e(A3),r (D8b)and a(A2)phases at temperatures between750and1300°C in the Co-Cr-Ni system were determined by differential scanning calorimetry and electron probe microanalysis.It was found that the c solidus and liquidus temperatures decrease with increasing Cr or Ni content and that the difference between them increases with increasing Cr content.The phase equilibria at800, 900,1000,1100,1200and1300°C were determined using two-or three-phase alloys,and the phase boundaries due to the magnetically induced phase separation in the c and e phases were also observed at850,800and750°C by the diffusion couple method.
Keywords differential scanning calorimetry(DSC),experimental phase equilibria,liquidus,ternary phase diagram
1.Introduction
Co-Cr-based alloys are widely used as biomaterials, magnetic materials,machine tool materials and high-tem-perature materials such as for aerospace engines and land-based turbines for power generation because of their excellent wear and corrosion resistance and weldability. The refractory elements Mo and W are often utilized as the major solid-solution strengtheners in both cast and wrought alloys,while Ni is used in wrought alloys to stabilize the face-centered cubic c(A1)phase and to suppress the transformation to the hexagonal-close-packed e(A3)phase in order to improve the workability.[1]The high-temperature strength of conventional Co-based superalloys strengthened by solid solution and carbide precipitation hardening is not so high compared with that of Ni-based superalloys strengthened by the c￠phase with the L12structure.Since the Co3(Al,W)c￠phase has recently been discovered,[2]Co-Al-W-based alloys with the c/c￠two-phase microstructure have potential as a new class of superalloys.[2-7]It has been reported that the addition of Ni is effective to increase the stability of the c￠phase[8]and that the oxidation resistance can be improved by the addition of Cr.[9]Therefore,the Co-Cr-Ni system is an important constituent system of Co-based alloys.In addition,Co-Cr-based sputtered?lm,consisting of ?ne precipitates of a Co-rich ferromagnetic e phase and a Cr-rich paramagnetic e matrix,is good material for magnetic recording media.This compositional modulation is one of the reasons for its excellent recording properties such as high coercivity and low noise properties.[10]It is considered that this compositional?uctuation is due to the magnetically induced phase separation in the Co-Cr phase diagram.[11-13] Therefore,investigations of the phase separation in the Co-Cr-based alloy systems are of importance.
The three sub-binary systems constituting the Co-Cr-Ni ternary system are shown in Fig.1.[13-15]It can be seen that a complete solid solution c(Co,Ni)is formed between Co and Ni at high temperatures and that both c Co and c Ni phases can contain a signi?cant amount of Cr in each binary system.The r(D8b)phase exists between the c Co and a Cr(A2)phases in the Co-Cr system.The phase equilibria in the Co-Cr-Ni system have been studied in various works.[16-24]There have been two versions of the phase diagram regarding the region around the r phase,as shown in Fig.1:Rideout et al.[16]have determined the isothermal section by optical microscopy and the x-ray diffraction(XRD)technique and diffusion couples (DCs)were used in the work by Jin.[21]
In this study,the phase equilibria including the phase separation in the Co-Cr-Ni system were experimentally inves-tigated using two-or three-phase alloys and the DC method;the solidus and liquidus temperatures were also measured.
2.Experimental Procedures
Co-Cr-Ni ternary and Cr-40Ni binary alloys were prepared by arc melting in an Ar atmosphere,where they were melted more than?ve times to obtain homogeneous ingots.Small pieces of specimens were sealed in quartz capsules evacuated and back?lled with Ar gas.
The solidus and liquidus temperatures of Co-Cr-Ni alloys were determined by differential scanning calorimetry (DSC),several pure metals being used for temperature calibration.The measurements were conducted using small pieces of specimens ranging from18to44mg at a heating rate of1°C/min in a He atmosphere,the solidus and liquidus temperatures being de?ned by the onset and peak
T.Omori,J.Sato,K.Shinagawa,I.Ohnuma,K.Oikawa, R.Kainuma,and K.Ishida,Department of Materials Science, Graduate School of Engineering,Tohoku University,Aoba-yama6-6-02,Sendai980-8579,Japan.Contact e-mail:omori@material.tohoku. ac.jp.
JPEDA V(2014)35:178–185 DOI:10.1007/s11669-014-0292-z 1547-7037óASM International
Fig.1Binary phase diagrams(at.%)[13-15]bonding the Co-Cr-Ni ternary system and isothermal section of the Co-Cr-Ni system at
1200°C,where the solid and dashed lines represent the phase boundaries reported in Ref16and21,
respectively
Fig.2(a)DSC heating curve of Co-20Cr-40Ni and(b)c soli-dus(solid symbol)and liquidus(open symbol)temperatures in Co-Cr-Ni alloys Table1Solidus and liquidus temperatures in Co-Cr-Ni alloys
Specimen,at.%Solidus temp.,°C Liquidus temp.,°C
Co-10Cr-10Ni1488
Co-10Cr-20Ni1482
Co-10Cr-30Ni1475
Co-10Cr-40Ni1469
Co-10Cr-50Ni1464
Co-10Cr-60Ni1457
Co-10Cr-70Ni1454
Co-10Cr-80Ni1449
Co-20Cr-10Ni14741480
Co-20Cr-20Ni14671473
Co-20Cr-30Ni14601465
Co-20Cr-40Ni14521458
Co-20Cr-50Ni14471453
Co-20Cr-60Ni14401446
Co-20Cr-70Ni14351441
Co-30Cr-10Ni14511460
Co-30Cr-20Ni14431451
Co-30Cr-30Ni14371445
Co-30Cr-40Ni14301437
Co-30Cr-50Ni14221430
Co-30Cr-60Ni14151422
Co-40Cr-10Ni14191432
Co-40Cr-20Ni14131425
Co-40Cr-30Ni14081418
Co-40Cr-40Ni14021411
Co-40Cr-50Ni13931402
temperatures in the heating curve,as shown in Fig.2(a),respectively.The liquidus temperature could be determined when the interval between the solidus and liquidus temper-atures is larger than 5°C in the present examination,because the temperature interval during the melting reaction was 5°C for pure Ni in this experimental condition.
The two-phase or three-phase Co-Cr-Ni alloys were annealed at 800-1300°C for 48-672h followed by water quenching,where homogenization at 1300°C was carried out before annealing at 800-1000°C.The composition in each phase was measured by electron probe microanalysis (EPMA)and determined by more than ?ve data calibrated by the ZAF correction using the pure elements as standards.The phase identi?cation was conducted by the XRD technique with Cu-K a radiation.
DCs were prepared to determine the magnetically induced phase separation.Co-(1-5)Ni and Co-(27-29.7)Cr-(1-10)Ni alloys were joined using a clamp consisting of two stainless steel disks and Mo bolts in evacuated quartz capsules at 1000°C for 2h.The prepared DCs were then sealed in quartz capsules and annealed at 750-850°C for 600-1000h,followed by water quenching.The composi-tion-penetration curves at the cross sections of the DCs were obtained by
EPMA.
Fig.3Back-scattered electron images of (a)Co-50Cr-15Ni,(b)Co-60Cr-33Ni and (c)Co-70Cr-4Ni alloys annealed at 900°C for 336h after homogenization at 1300°C and (d)Co-60Cr-33Ni alloy annealed at 1100°C for 120
h
Fig.4X-ray diffraction pattern of (a)Co-50Cr-15Ni and (b)Co-55Cr-25Ni alloys annealed at 1200°C
3.Results
3.1Solidus and Liquidus Temperatures
A DSC heating curve for the melting reaction of Co-20Cr-40Ni alloy is shown in Fig.2(a),and the c solidus and liquidus temperatures of all the Co-Cr-Ni alloys are listed in Table1and plotted in Fig.2(b)with binary data,[25] where the liquidus temperature of Co-10Cr-Ni alloys cannot be determined because of the small difference between the solidus and liquidus temperatures.It can be seen in Fig.2(b) that both the temperatures decrease with increasing Cr or Ni contents and that the difference between them increases with increasing Cr content.
Table2Equilibrium compositions of Co-Cr-Ni alloys
Temperature,
°C Sample Time,h
Composition,at.%
c r a
Cr Ni Cr Ni Cr Ni
1300Co-50Cr-5Ni4845.9 5.053.5 3.9 Co-50Cr-15Ni4845.616.457.311.3
Co-55Cr-25Ni4848.529.660.820.6
Co-60Cr-33Ni4850.942.164.329.7
Cr-40Ni4852.048.066.933.1 1200Co-50Cr-5Ni16843.0 6.456.2 3.9
Co-50Cr-15Ni16845.017.058.710.1
Co-55Cr-25Ni16847.730.264.018.4
Co-60Cr-33Ni16850.042.968.925.4
Cr-40Ni7250.949.172.627.4
Co-70Cr-4Ni7264.1 4.570.6 3.8 1100Co-50Cr-5Ni12040.9 6.455.5 3.7
Co-50Cr-15Ni12043.218.058.510.1
Co-55Cr-25Ni12046.531.962.518.8
Co-60Cr-33Ni12048.644.177.018.1
Cr-40Ni12048.551.584.615.4
Co-70Cr-4Ni12066.2 4.678.1 2.8
Co-70Cr-10Ni12065.611.676.57.6 1000Co-50Cr-5Ni240(a)39.77.256.2 3.6
Co-50Cr-15Ni240(a)41.619.759.010.0
Co-55Cr-25Ni240(a)44.334.062.618.4
Co-60Cr-33Ni240(a)45.545.789.47.2
Cr-40Ni240(a)45.754.392.57.5
Co-70Cr-4Ni240(a)66.6 4.485.0 1.7
Co-70Cr-10Ni240(a)65.811.685.1 4.4 900Co-50Cr-5Ni336(a)37.4(b)7.2(b)55.2 3.7
Co-50Cr-15Ni336(a)39.519.258.510.5
Co-55Cr-25Ni336(a)41.336.262.117.8
Co-60Cr-33Ni336(a)41.948.195.3 2.9
Cr-40Ni336(a)42.157.997.6 2.4
Co-70Cr-4Ni336(a)65.5 4.090.00.8
Co-70Cr-10Ni336(a)64.311.991.7 1.8 800Co-50Cr-5Ni672(a)39.1(b) 6.8(b)54.5 4.0
Co-50Cr-15Ni672(a)42.917.556.211.6
Co-55Cr-25Ni672(a)40.135.162.717.095.3 1.7
Cr-40Ni672(a)39.360.797.7 2.3
Co-60Cr-33Ni672(a)39.150.495.0 3.4
Co-70Cr-4Ni672(a)64.7 4.690.90.9
Co-70Cr-10Ni672(a)63.912.094.9 1.2
(a)Heat treatment at1300°C was carried out before equilibrium heat treatment
(b)e phase
Fig.5Isothermal sections of Co-Cr-Ni system at(a)1300°C,(b)1200°C,(c)1100°C,(d)1000°C,(e)900°C and(f)800°C
3.2Phase Equilibria at Temperatures Between
800and 1300°C
Figure 3shows the back-scattered electron (BSE)images of typical two-phase microstructures in Co-50Cr-15Ni,(b)Co-60Cr-33Ni and (c)Co-70Cr-4Ni alloys annealed at 900°C after homogenization at 1300°C and (d)Co-60Cr-33Ni alloy annealed at 1100°C,and the XRD pro?les of Co-50Cr-15Ni and Co-55Cr-25Ni alloys annealed at 1200°C are presented in Fig.4.All data on the phase equilibria of Co-Cr-Ni and Cr-Ni alloys at temperatures between 800and 1300°C acquired by EPMA are summarized in Table 2and plotted in Fig.5.The c phase is equilibrated only with the a phases at 1300°C,while the c ,r and a phases and the c ,e ,r and a phases are equilibrated at 1000-1200°C and at 800and 900°C,respectively.Judging from the chemical compo-sitions,the bright and dark contrast regions in Fig.3(a)-(d)are considered to be the c and r phases,the c and a phases,the r and a phases and the c and a phases,respectively.A ?ne c +a two-phase structure with some habit planes is observed in the Co-60Cr-33Ni alloy annealed at 900°C (Fig.3b),and the same alloy annealed at 1100°C (Fig.3d)shows the coarse microstructure.It is considered that the c phase precipitates in the a phase at 900or 1100°C due to the much lower solubility of Ni and Co in the a phase at these temperatures than that at higher temperatures and that the Widmansta ¨tten morphology is the characteristic microstructural feature of this alloy annealed in this temperature range.No three-phase equi-libria were obtained except at 800°C in the present study,but the Co-50Cr-15Ni and Co-55Cr-25Ni alloys have the c +r and c +a two-phase structures at 1200°C (Fig.4
),
Fig.6DC of Co-3Ni and Co-29.1Cr-3Ni annealed at 800°C for 600h and its concentration pro?le
Table 3Equilibrium compositions determined by diffusion couples in Co-Cr-Ni alloys
Temperature,°C Diffusion couple Time,h Composition,at.%
c ferro
c para
e para
Cr Ni Cr Ni Cr
Ni
850
Co1Ni/Co29.7Cr1Ni 720 2.4 1.18.4 1.1Co5Ni/Co28.5Cr5Ni 600 2.0 5.08.9 5.2Co10Ni/Co27Cr10Ni 600 1.310.48.010.4Co1Ni/Co29.7Cr1Ni 72025.7 1.127.7 1.1
800
Co1Ni/Co29.7Cr1Ni 1000 2.0 1.015.0 1.1Co3Ni/Co29.1Cr3Ni 600 1.2 3.110.9 3.1Co5Ni/Co28.5Cr5Ni 600 1.7 5.210.5 5.2Co10Ni/Co27Cr10Ni 600 1.4
10.4
9.710.4Co1Ni/Co29.7Cr1Ni 100021.2 1.025.9 1.0Co3Ni/Co29.1Cr3Ni 60023.0 3.228.3 3.2Co5Ni/Co28.5Cr5Ni 60025.0 5.228.0 5.3750
Co1Ni/Co29.7Cr1Ni 600 1.4 1.017.6 1.0
Co3Ni/Co29.1Cr3Ni 600 1.4 3.212.5 3.2Co5Ni/Co28.5Cr5Ni 600 1.5 5.2
14.4 5.2Co3Ni/Co29.1Cr3Ni 60020.3 3.223.2 3.0Co5Ni/Co28.5Cr5Ni
600
21.6
5.2
26.8 5.2
respectively,meaning that a three-phase region exists between these alloy contents,as shown in Fig.5.The shape of phase boundaries in the Co-Cr-Ni system is not similar to that in Ref 21but to that in Ref 16although the three-phase triangle exists in the lower Ni content region.The difference in the phase equilibria of the Cr-Ni binary system between the experimental data in this study and those in Ref 15is less than about 2at.%.
3.3Phase Separation Observed by the Diffusion Couple
Method Figure 6(a)shows the BSE image of a Co-3Ni/Co-29.1Cr-3Ni DC specimen annealed at 800°C for 600h.The
boundaries are formed in the diffusion zone and the concentration-penetration curve across the boundaries mea-sured by EPMA is shown in Fig.6(b).The composition gaps are observed,corresponding to the boundaries with contrast steps in the BSE image,and the compositions determined by extrapolating the composition-penetration pro?le to the interfacial boundaries at 850,800and 750°C are listed in Table 3and plotted in Fig.7.It is considered from these compositional data and the previously reported Co-Cr binary phase diagram [13]that the left,center and right regions are the ferromagnetic c phase (c ferro ),the paramagnetic c phase (c para )and the paramagnetic e phase (e para ),respectively.These phase boundaries are due to the magnetically induced phase separation,as observed in several Co-X systems including Co-Cr,[11,13]Co-V ,[26]Co-W,[27,28]Co-Ge [29]and Co-Mo.[30]Further experiments on phase equilibria using two-phase alloys are thought to be necessary to determine the phase boundaries with a higher degree of accuracy.
4.Summary
The c solidus and liquidus temperatures of Co-Cr-Ni alloys were measured by DSC and it was found that they decreased with increasing Cr or Ni content and that the difference between them increased with increasing Cr content.The isothermal sections at 800,900,1000,1100,1200and 1300°C were determined in the whole compositional range of the Co-Cr-Ni system using two-or three-phase alloys.In addition,the phase boundaries (c ferro /c para ,c ferro /e para ,c para /e para )due to magnetically induced phase separation were observed at 750,800and 850°C by the DC method.
Acknowledgments
This work was supported by the New Energy and Industrial Technology Development Organization (NEDO).Support from a Grant-in-Aid for Scienti?c Research from JSPS and a Grant for Excellent Graduate Schools from MEXT is also acknowledged.
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Motivation, Determination and Dedication What makes an original contributor in science is often not only ability, but also something else, something apparently intangible, and not easily detected. This extra something lies deep within the individual and needs to be nurtured and tested. Motivation is a personal trait that is primarily instilled by seniors such as teachers or parents. An important aspect in developing motivation is the setting of goals. A person probably has set long-range goals, or at this point more like dreams, such as winning the Nobel Prize. This is great as long as the individual is realistically working toward short-range also. These are the day-to-day accomplishments that really make working hard seem fun. Proficiency in anything requires a great deal of determination and self-discipline. In addition, a person’s ability to cope with frustration is also an important factor in one’s life career. Repeated failures at making experiments may be too much for many talented would-be scientists. The determination to continue, with the realization that everything worthwhile takes a great deal of patience, is an essential requirement. These factors, together with inherent dedication, will bring about the realization of one’s aspirations. Through all this it is not the triumph but he struggle that brings about the complete personal satisfaction in knowing that you as a scientist have given your all.
国科发火〔2008〕172号 关于印发《高新技术企业认定管理办法》的通知 各省、自治区、直辖市、计划单列市科技厅（局）、财政厅（局）、国家税务局、地方税务局： 根据《中华人民共和国企业所得税法》、《中华人民共和国企业所得税法实施条例》的有关规定，经国务院批准，现将《高新技术企业认定管理办法》及其附件《国家重点支持的高新技术领域》印发给你们，请遵照执行。 附件：高新技术企业认定管理办法 科技部财政部国家税务总局 二ＯＯ八年四月十四日 Administrative Measures for the Determination of High and New Tech Enterprises (No. 172 [2008] of the Ministry of Science and Technology) The science and technology departments (bureaus), finance departments (bureaus), offices of the State Administration of Taxation and local taxation bureaus of all provinces, autonomous regions, municipalities directly under the Central Government and cities under separate state planning, In accordance with the Enterprise Income Tax Law of the People’s Republic of China and Regulation on the Implementation of the Enterprise Income Tax Law of the People’s Republic of China, and upon approval of the State Council, the Administrative Measures for the Determination of High and New Tech Enterprises and the annex, i.e. the High and New Tech Fields under the Key Support of the State, are hereby printed and distributed to you for your compliance. Annex: Administrative Measures for the Determination of High and New Tech Enterprises Ministry of Science and Technology, Ministry of Finance, State —1—
The POWER of determination The little country schoolhouse was heated by an old-fashioned , pot-belled stove . A little boy had the job of coming to school early each day to start the fire and warm the room before his teacher and his classmates arrived . One morning they arrived to find the schoolhouse engulfed in flames . They dragged the unconscious little boy out of the flaming building more dead than alive . He had major burns over the lower half of his bady and was taken to the nearby county hospital . From his bed the dreadfully burned , semi-conscious little boy faintly heard the doctor told his mother that her son would surely die - which was for the best , really - for the terrible fire had devastated the lower half of his body . But the brave boy didn't want to die . He made up his mind that he would survive . Somehow , to the amazement of the physician , he did survive . When the mortal danger was past , he again heard the doctor and his mother speaking quietly . The mother was told that since the fire had destroyed so much flesh in the lower part of his body , it would almost be better if he had died , since he was doomed to be a lifetime cripple with no use at all of his lower limbs . Once more the brave boy made up his mind . He would not be a cripple . He would walk . But unfortunately , from the waist down he no motor ability . His thin legs dangled there , all but lifeless . Ultimately he was released from the hospital . Every day his mother would massage his little legs , but there was no feeling , no control , nothing . Yet his determination that he would walk was as strong as ever . When he wasn't in bed , he was confined to a wheelchair . One sunny day his mother wheeled him out into the yard to get some fresh air . This day , instead of sitting there , he therw himself from the chair . He pulled himself across the grass , dragging his legs behind him . He worked his way to the white picket fence bordering their lot . With great effort , he raised himself up on the fence . Then , stake by stake , he began dragging himself along the fence , resolved that he would walk . He started to do this every day until he beside the fence . There was nothing he wanted more than to develop life on those legs . Ultimately , through his daily massages , his iron persistence and his resolute determination , he did develop the ability to stand up , then to walk haltingly , then to walk by himself - and then to run .
SAP自动科目确定Account Determination 理论概述： Account Determination：通过设定实现物料异动是自动决定会计凭证产生的科目 Automatic Account Determination涉及如下操作： Goods receipt Goods issue Transfer posting Incoming invoice Price change Debit/credit Material Account maintenance 配置介绍： 1、OBYC/OMWB Materials ManagementàValuation and Account AssignmentàAccountDeterminationàAccount Determination WithoutWizardàConfigure Automatic Postings 如下图： 在物料异动时由以下涉及到的不同条件决定借贷方分别抛什么样的科目， ① Chart of Accounts: ② (valuation modification)Valuation Grouping code: 当valuation grouping code被激活，可以通过将不同的valuation area进行分组得到的grouping code座位参数来决定G/L account no. ③ Valuation Class:由物料决定 ④ Transaction: Posting transactions 在系统中是固定的，用来控制是否抛入存货，差异科目，GRIR清帐科目等等。
á921? WATER DETERMINATION Many Pharmacopeial articles either are hydrates or contain water in adsorbed form. As a result, the determination of the water content is important in demonstrating compliance with the Pharmacopeial standards. Generally one of the methods giv-en below is called for in the individual monograph, depending upon the nature of the article. In rare cases, a choice is allowed between two methods. When the article contains water of hydration, Method I (Titrimetric), Method II (Azeotropic), or Method III (Gravimetric) is employed, as directed in the individual monograph, and the requirement is given under the heading Water.The heading Loss on Drying (see Loss on Drying á731?) is used in those cases where the loss sustained on heating may be not entirely water. METHOD I (TITRIMETRIC) Determine the water by Method Ia, unless otherwise specified in the individual monograph. Method Ia (Direct Titration) Principle—The titrimetric determination of water is based upon the quantitative reaction of water with an anhydrous solu-tion of sulfur dioxide and iodine in the presence of a buffer that reacts with hydrogen ions. In the original titrimetric solution, known as Karl Fischer Reagent, the sulfur dioxide and iodine are dissolved in pyridine and methanol. The test specimen may be titrated with the Reagent directly, or the analysis may be carried out by a residual titra-tion procedure. The stoichiometry of the reaction is not exact, and the reproducibility of a determination depends upon such factors as the relative concentrations of the Reagent ingredients, the nature of the inert solvent used to dissolve the test speci- men, and the technique used in the particular determination. Therefore, an empirically standardized technique is used in order to achieve the desired accuracy. Precision in the method is governed largely by the extent to which atmospheric moisture is excluded from the system. The titration of water is usually carried out with the use of anhydrous methanol as the solvent for the test specimen. In some cases, other suitable solvents may be used for special or unusual test specimens. In these cases, the addition of at least 20% of methanol or other primary alcohol is recommended. Apparatus—Any apparatus may be used that provides for adequate exclusion of atmospheric moisture and determination of the endpoint. In the case of a colorless solution that is titrated directly, the endpoint may be observed visually as a change in color from canary yellow to amber. The reverse is observed in the case of a test specimen that is titrated residually. More commonly, however, the endpoint is determined electrometrically with an apparatus employing a simple electrical circuit that serves to impress about 200 mV of applied potential between a pair of platinum electrodes immersed in the solution to be titrated. At the endpoint of the titration a slight excess of the reagent increases the flow of current to between 50 and 150microamperes for 30 s to 30 min, depending upon the solution being titrated. The time is shortest for substances that dissolve in the reagent. With some automatic titrators, the abrupt change in current or potential at the endpoint serves to close a sole-noid-operated valve that controls the buret delivering the titrant. Commercially available apparatus generally comprises a closed system consisting of one or two automatic burets and a tightly covered titration vessel fitted with the necessary electro-des and a magnetic stirrer. The air in the system is kept dry with a suitable desiccant, and the titration vessel may be purged by means of a stream of dry nitrogen or current of dry air. Reagent—Prepare the Karl Fischer Reagent as follows. Add 125g of iodine to a solution containing 670 mL of methanol and 170 mL of pyridine, and cool. Place 100 mL of pyridine in a 250-mL graduated cylinder, and, keeping the pyridine cold in an ice bath, pass in dry sulfur dioxide until the volume reaches 200 mL. Slowly add this solution, with shaking, to the cooled iodine mixture. Shake to dissolve the iodine, transfer the solution to the apparatus, and allow the solution to stand overnight before standardizing. One mL of this solution when freshly prepared is equivalent to approximately 5 mg of water, but it dete-riorates gradually; therefore, standardize it within 1 h before use, or daily if in continuous use. Protect from light while in use.Store any bulk stock of the reagent in a suitably sealed, glass-stoppered container, fully protected from light, and under refrig-eration. For determination of trace amounts of water (less than 1%), it is preferable to use a Reagent with a water equivalency factor of not more than 2.0, which will lead to the consumption of a more significant volume of titrant. A commercially available, stabilized solution of Karl Fischer type reagent may be used. Commercially available reagents con-taining solvents or bases other than pyridine or alcohols other than methanol may be used also. These may be single solutions or reagents formed in situ by combining the components of the reagents present in two discrete solutions. The diluted Re-agent called for in some monographs should be diluted as directed by the manufacturer. Either methanol or other suitable solvent, such as ethylene glycol monomethyl ether, may be used as the diluent. Test Preparation—Unless otherwise specified in the individual monograph, use an accurately weighed or measured amount of the specimen under test estimated to contain 2–250 mg of water. The amount of water depends on the water equivalency factor of the Reagent and on the method of endpoint determination. In most cases, the minimum amount of specimen, in mg, can be estimated using the formula: FCV / KF
Journal of Chromatography B,900 (2012) 94–99 Contents lists available at SciVerse ScienceDirect Journal of Chromatography B j o u r n a l h o m e p a g e :w w w.e l s e v i e r.c o m /l o c a t e /c h r o m b Short communication Determination of phenylethanolamine A in animal hair,tissues and feeds by reversed phase liquid chromatography tandem mass spectrometry with QuEChERS Ming-Xia Zhang a ,Cun Li a ,b ,Yin-Liang Wu c ,? a Hebei University of Engineering,Handan 056038,PR China b Tianjin Agricultural University,Tianjin 300380,PR China c Ningbo Academy of Agricultural Sciences,Ningbo 315040,PR China a r t i c l e i n f o Article history: Received 6March 2012Accepted 24May 2012 Available online 2 June 2012 Keywords: Phenylethanolamine A QuEChERS Hair Animal tissues Animal feeds LC–MS/MS a b s t r a c t A simple,sensitive and reliable analytical method was developed for the determination of a new beta-agonist phenylethanolamine A in animal hair,tissues and animal feeds by ultra high performance liquid chromatography–positive electrospray ionization tandem mass spectrometry (UHPLC–ESI-MS/MS)with QuEChERS.Samples were extracted with acetonitrile/water (80:20,v/v).The extract was puri?ed through QuEChERS method,then was dried with nitrogen and residues were redissolved in mobile phase for hair sample or directly diluted with 0.1%formic acid in water for other samples,and analyzed by LC–MS/MS on a Waters Acquity BEH C 18column with 0.1%formic acid in water/methanol as mobile phase with gradient elution.The samples were quanti?ed using phenylethanolamine A-D 3as internal standards.The pro-posed method was validated according to the European Commission Decision 2002/657/EC determining speci?city,decision limit (CC ?),detection capability (CC ?),recovery,precision,linearity,robustness and stability.The CC ?values ranged from 0.10to 0.26?g/kg.The CC ?values ranged from 0.20to 0.37?g/kg.The mean recoveries of 95.4–108.9%with intra-day CVs of 2.2–5.6%and inter-day CVs of 3.1–6.2%were obtained.The method is demonstrated to be suitable for the determination of phenylethanolamine A in animal hair,tissues and animal feeds.The total time required for the analysis of one sample except animal hair sample,including sample preparation,was about 25min. ? 2012 Elsevier B.V. All rights reserved. 1.Introduction Beta-agonists are originally used in the therapeutic treatment of asthma and preterm labor in humans [1].However,these com-pounds are also misused as growth promoters in livestock by diverting nutrients from fat deposition to the production of muscle tissues in animals [2].This misuse had caused some severe acci-dental poisonings in humans [3,4].Therefore,all beta-agonists are banned as feed additives for growth promotion in animals in China and EU [5,6].With the crackdown of banned beta-agonists,such as clenbuterol,salbutamol and ractopamine,a new beta-agonist named phenylethanolamine A has been illegally used in livestock in China (Fig.1)[7].In order to control the use of phenylethanolamine A,speci?c and sensitive methods for identifying and quantifying of phenylethanolamine A in animal hair,tissues and animal feeds are required. Although gas chromatography–mass spectrometry (GC–MS)[8–11]and liquid chromatography–mass spectrometry (LC–MS) ?Corresponding author.Tel.:+8657487928060;fax:+8657487928062.E-mail address:wupaddy?eld@https://www.doczj.com/doc/6f1366583.html, (Y.-L.Wu). [12–17]methods have been developed to identify beta-agonists in biological samples,there are little literatures on identi?cation of phenylethanolamine A in animal tissues and feeds [7,18].A LC–MS/MS method had been recently developed by Sun and Yan in swine muscle [7].However,the pre-treatment procedure of the method was very complicated and time-consuming because the combination of enzymatic hydrolysis,liquid–liquid extraction and solid phase extraction (SPE)were used to cleanup.Therefore,rapid,speci?c and sensitive methods for the identi?cation and quanti?-cation of phenylethanolamine A in hair,animal tissues and feeds are required. The QuEChERS method was previously used by Anastassiades et al.for the determination of pesticides in fruit and vegetable samples with primary and secondary amine (PSA)as the base sor-bent [19].The method has already received worldwide acceptance because of the simplicity and high throughput enabled a labora-tory to process signi?cantly a large number of samples in a given time.Moreover,the method had recently been used for the deter-mination of veterinary drug residue and mycotoxins [20,21].Due to high ef?ciency of QuEChERS,it is necessary to develop QuECh-ERS method for phenylethanolamine A in animal hair,tissues and feeds. 1570-0232/$–see front matter ? 2012 Elsevier B.V. All rights reserved.https://www.doczj.com/doc/6f1366583.html,/10.1016/j.jchromb.2012.05.030
第4单元 价格决定（Price Determination）
经济学BA330 4.1 定义（Definition） 市场上所有商品以当时价格完全售出后就会出现均衡价格。 卖者以均衡价格买入市场的商品正由买者购买时出现均衡数量。 1.50 1.20 Pe 1.00 Q e 均衡价格和均衡数量 说明：P e, Q e = 市场商品全部售出时的均衡量 D < S = 剩余 D1 > S1 = 短缺 4.2 对均衡价格和数量的影响（Effect on the Equilibrium Price and Quantity） 4.2.1 需求条件变动（但供应量不变）（When Conditions of Demand Changed (With Supply Unchanged) 如果需求条件发生变动使需求曲线左移，将出现新的均衡价格和数量，如下图(i) 所示。
BA330 经济学 Q Q (i) 需求移动 (ii) 供应移动 4.2.2 供应条件变动时（需求条件不变）When Conditions of Supply Changed (With Demand Unchanged) 如果需求条件发生变动使曲线左移，会引起新的均衡价格和数量，如上图(ii) 所示。 4.2.3需求和供应两种条件都发生变动时（When Both Conditions of Demand and Supply Changed ） 如果需求和供应两种条件都发生变动，则只有当我们知道以下条件时才能决定均衡价格和数量： - 移动方向（左或者右） - 移动幅度（距离） - 需求和供应曲线的坡度 4.2.4国家征收间接税时（When Government Imposes an Indirect Tax ） 征收间接税会减少一个企业准备以每种不同价格进行供给的数量，下表示出这一影响。 D 1 P P e P P e
In 1883, a creative engineer named John Roebling was inspired to build a spectacular[壮观的] bridge connecting New York with Long Island. However bridge-building experts throughout the world thought that this was an impossible feat and told Roebling to forget the idea. Roebling could not ignore the vision he had in his mind of this bridge. After much discussion, he managed to convince his son Washington, an up-and-coming[初崭头角的] engineer, that the bridge in fact could be built. Working together for the first time, the father and son developed concepts of how it could be accomplished and how the obstacles[障碍] could be overcome. They hired their crew and began to build their dream bridge. The project started well, but when it was only a few months underway a tragic accident on the site took the life of John Roebling. Washington was injured, unable to walk or talk or even move. Everyone had negative[负面的] comments and felt that the project should be scrapped[抛弃] since the Roeblings were the only ones who knew how the bridge could be built. In spite of his handicap[身体的不便] Washington was never discouraged and still had a burning desire to complete the bridge and his mind was still as sharp as ever. He tried to inspire and pass on his enthusiasm[激情] to some of his friends, but they were too daunted[气馁的] by the task. As he lay on his bed in his hospital room, with the sunlight streaming through the windows, a gentle breeze blew the flimsy[薄薄的] white curtains apart and he was able to see the sky and the tops of the trees outside for just a moment. It seemed that there was a message for him not to give up. Suddenly an idea hit him. All he could do was move one finger and he decided to make the best use of it. By moving this, he slowly developed a code of communication with his wife. He touched his wife's arm with that finger, indicating to her that he wanted her to call the engineers again. Then he used the same method of tapping her arm to tell the engineers what to do. For 13 years Washington tapped out his instructions with his finger on his wife's arm, until the bridge was finally completed. Today the spectacular Brooklyn Bridge stands in all its glory as a tribute to the triumph of one man's indomitable[不屈不挠的] spirit and his determination[坚定] not to be defeated by circumstances.