• Title/Summary/Keyword: Al substitution

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High-Pressure Synthesis and Chemistry of Amphibole Solid Solutions along the Joint Tremolite-Tschermakite (투각섬석-처마카이트 각섬석 고용체의 고압합성 및 화학적 성질)

  • 조문섭
    • Journal of the Mineralogical Society of Korea
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    • v.3 no.1
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    • pp.1-6
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    • 1990
  • Clacic amphiboles along the tremolite (Tr)-tschermakite(Ts) joint were synthesized using a piston-cylinder appratus. At 750-85$0^{\circ}C$and 12-2 kb, amphibole+corundum coexist with zoisite($\pm$talc, chlorite, and Mg-staurolite), but with anorthite($\pm$cholorite, spinel, pyroxenes, and sapphirine) at lower P. At 90$0^{\circ}C$, amphibole+corundum+clinopyroxene($\pm$anorthite, forsterite, sapphirine, and garnet) are stable over the P range 12-18 kb. These amphibole-bearing assemblages are replaced at high P by clcinopyroxene+talc+chlorite+zoisite at 650-75$0^{\circ}C$, and at higher temperatures by garnet+clinopyroxene($\pm$zoisite, orthopyroxene, and Mg-staurolite). Synthetic amphiboles with Ts>~45 mol% contain as much as 0.15 excess cations per formula unit(pfu) based on 23 oxygens(anhydrous formula), whereas less tschermakitic ones are deficient in cation occupancy by up to 0.18 pfu. This trend is attributed to the 야/trioctahedral substitution in Ca-amphiboles. Compositions of synthetic amphiboles display systematic changes with P and T governed by coexisting mineral assemblages. The Ts content (=[8-Si-Na]/2) increases with increasing T( Ts/ T=~0.1 nik% K-1) in the range 750-85$0^{\circ}C$, but remains nearly constant at 850-90$0^{\circ}C$. Pressure dramatically affects the Ts content of Ca-amphiboles:it increases with P at 8-12 kb( Ts/ T=2-3 mol% K-1), but significantly decreases at 12-21 kb( Ts/ P=-2.5 mol% Kb-1). Hence, the most tschermakitic amphiboles, containing 60$\pm$5 mol % Ts, or 1.2$\pm$0.1 tetrahedral Al, occur at 12 kb and 850-90$0^{\circ}C$. Compositions of Ca-amphiboles defined by a simple reaction, 3 Tr+2 zoisite+7 corundum+H2O=5 Ts, are reversed and used to estimate thermodynamic parameters of tschermakite assuming ideal mixing of Tr-Ts solid solutions. Predicted standard molal entropy and enthalpy of tschermakite are : S$^{\circ}$of Tr-Ts solid solutions. Predicted standard molal entropy and enthalpy of tschermakite are : S$^{\circ}$=566.9$\pm$13.7 J mol-1K, -1and H$^{\circ}$=-12518.36$\pm$15.17 kJ mol.-1

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Changes in the Linear Compressibility and Bulk Modulus of Natural Stilbite Under Pressure with Varying Pressure-Transmitting Media (천연 스틸바이트의 압력전달매개체에 따른 선형압축률 및 체적탄성률 비교 연구)

  • Hwang, Huijeong;Lee, Hyunseung;Lee, Soojin;Jung, Jaewoo;Lee, Yongmoon
    • Korean Journal of Mineralogy and Petrology
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    • v.35 no.3
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    • pp.367-376
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    • 2022
  • This study is a preliminary step to understand the reaction between various liquids and zeolite in the subduction zone environment. Stilbite, NaCa4(Al9Si27)O72·28(H2O), was selected and high pressure study was conducted on compressional behavior by the pressure-transmitting medium (PTM). Water and NaHCO3 solution that can exist in the subduction zone was used as PTM, and samples were pressurized from ambient to a maximum of 2.5 GPa. Below 1.0 GPa, both experiments show a low linear compressibility in the range of 0.001 to 0.004 GPa-1 and a high bulk modulus of 220(1) GPa. This is presumably because the structure of the stilbite becomes very dense due to insertion of water molecules or cations into the channel. On the other hand, at 1.0 GPa or higher, the trends of the two experiments are different. In the water run, the linear compressibility of the c-axis is increased to 0.006(1) GPa-1. In the NaHCO3 run, the linear compressibility of the b- and c-axis is increased to 0.006(1) GPa-1. The bulk modulus after 1.0 GPa shows values of 40(1) and 52(7) GPa in water and NaHCO3 run, respectively, confirming that stilbite becomes more compressible than that before 1.0 GPa. It is caused by the migration of cations and water molecules inside the channel, as the water molecules in the PTM start to freeze and stop to insert toward the channel at 1.0 GPa or more. In the NaHCO3 run, it is assumed that the distribution of extra-framework species inside the structure is changed by substitution of the Na+ cation. It can be expected from tendency of the relative intensity ratio of the (001) and (020) peaks which show a different from that of the water run.

The Relations between Financial Constraints and Dividend Smoothing of Innovative Small and Medium Sized Enterprises (혁신형 중소기업의 재무적 제약과 배당스무딩간의 관계)

  • Shin, Min-Shik;Kim, Soo-Eun
    • Korean small business review
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    • v.31 no.4
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    • pp.67-93
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    • 2009
  • The purpose of this paper is to explore the relations between financial constraints and dividend smoothing of innovative small and medium sized enterprises(SMEs) listed on Korea Securities Market and Kosdaq Market of Korea Exchange. The innovative SMEs is defined as the firms with high level of R&D intensity which is measured by (R&D investment/total sales) ratio, according to Chauvin and Hirschey (1993). The R&D investment plays an important role as the innovative driver that can increase the future growth opportunity and profitability of the firms. Therefore, the R&D investment have large, positive, and consistent influences on the market value of the firm. In this point of view, we expect that the innovative SMEs can adjust dividend payment faster than the noninnovative SMEs, on the ground of their future growth opportunity and profitability. And also, we expect that the financial unconstrained firms can adjust dividend payment faster than the financial constrained firms, on the ground of their financing ability of investment funds through the market accessibility. Aivazian et al.(2006) exert that the financial unconstrained firms with the high accessibility to capital market can adjust dividend payment faster than the financial constrained firms. We collect the sample firms among the total SMEs listed on Korea Securities Market and Kosdaq Market of Korea Exchange during the periods from January 1999 to December 2007 from the KIS Value Library database. The total number of firm-year observations of the total sample firms throughout the entire period is 5,544, the number of firm-year observations of the dividend firms is 2,919, and the number of firm-year observations of the non-dividend firms is 2,625. About 53%(or 2,919) of these total 5,544 observations involve firms that make a dividend payment. The dividend firms are divided into two groups according to the R&D intensity, such as the innovative SMEs with larger than median of R&D intensity and the noninnovative SMEs with smaller than median of R&D intensity. The number of firm-year observations of the innovative SMEs is 1,506, and the number of firm-year observations of the noninnovative SMEs is 1,413. Furthermore, the innovative SMEs are divided into two groups according to level of financial constraints, such as the financial unconstrained firms and the financial constrained firms. The number of firm-year observations of the former is 894, and the number of firm-year observations of the latter is 612. Although all available firm-year observations of the dividend firms are collected, deletions are made in the case of financial industries such as banks, securities company, insurance company, and other financial services company, because their capital structure and business style are widely different from the general manufacturing firms. The stock repurchase was involved in dividend payment because Grullon and Michaely (2002) examined the substitution hypothesis between dividends and stock repurchases. However, our data structure is an unbalanced panel data since there is no requirement that the firm-year observations data are all available for each firms during the entire periods from January 1999 to December 2007 from the KIS Value Library database. We firstly estimate the classic Lintner(1956) dividend adjustment model, where the decision to smooth dividend or to adopt a residual dividend policy depends on financial constraints measured by market accessibility. Lintner model indicates that firms maintain stable and long run target payout ratio, and that firms adjust partially the gap between current payout rato and target payout ratio each year. In the Lintner model, dependent variable is the current dividend per share(DPSt), and independent variables are the past dividend per share(DPSt-1) and the current earnings per share(EPSt). We hypothesized that firms adjust partially the gap between the current dividend per share(DPSt) and the target payout ratio(Ω) each year, when the past dividend per share(DPSt-1) deviate from the target payout ratio(Ω). We secondly estimate the expansion model that extend the Lintner model by including the determinants suggested by the major theories of dividend, namely, residual dividend theory, dividend signaling theory, agency theory, catering theory, and transactions cost theory. In the expansion model, dependent variable is the current dividend per share(DPSt), explanatory variables are the past dividend per share(DPSt-1) and the current earnings per share(EPSt), and control variables are the current capital expenditure ratio(CEAt), the current leverage ratio(LEVt), the current operating return on assets(ROAt), the current business risk(RISKt), the current trading volume turnover ratio(TURNt), and the current dividend premium(DPREMt). In these control variables, CEAt, LEVt, and ROAt are the determinants suggested by the residual dividend theory and the agency theory, ROAt and RISKt are the determinants suggested by the dividend signaling theory, TURNt is the determinant suggested by the transactions cost theory, and DPREMt is the determinant suggested by the catering theory. Furthermore, we thirdly estimate the Lintner model and the expansion model by using the panel data of the financial unconstrained firms and the financial constrained firms, that are divided into two groups according to level of financial constraints. We expect that the financial unconstrained firms can adjust dividend payment faster than the financial constrained firms, because the former can finance more easily the investment funds through the market accessibility than the latter. We analyzed descriptive statistics such as mean, standard deviation, and median to delete the outliers from the panel data, conducted one way analysis of variance to check up the industry-specfic effects, and conducted difference test of firms characteristic variables between innovative SMEs and noninnovative SMEs as well as difference test of firms characteristic variables between financial unconstrained firms and financial constrained firms. We also conducted the correlation analysis and the variance inflation factors analysis to detect any multicollinearity among the independent variables. Both of the correlation coefficients and the variance inflation factors are roughly low to the extent that may be ignored the multicollinearity among the independent variables. Furthermore, we estimate both of the Lintner model and the expansion model using the panel regression analysis. We firstly test the time-specific effects and the firm-specific effects may be involved in our panel data through the Lagrange multiplier test that was proposed by Breusch and Pagan(1980), and secondly conduct Hausman test to prove that fixed effect model is fitter with our panel data than the random effect model. The main results of this study can be summarized as follows. The determinants suggested by the major theories of dividend, namely, residual dividend theory, dividend signaling theory, agency theory, catering theory, and transactions cost theory explain significantly the dividend policy of the innovative SMEs. Lintner model indicates that firms maintain stable and long run target payout ratio, and that firms adjust partially the gap between the current payout ratio and the target payout ratio each year. In the core variables of Lintner model, the past dividend per share has more effects to dividend smoothing than the current earnings per share. These results suggest that the innovative SMEs maintain stable and long run dividend policy which sustains the past dividend per share level without corporate special reasons. The main results show that dividend adjustment speed of the innovative SMEs is faster than that of the noninnovative SMEs. This means that the innovative SMEs with high level of R&D intensity can adjust dividend payment faster than the noninnovative SMEs, on the ground of their future growth opportunity and profitability. The other main results show that dividend adjustment speed of the financial unconstrained SMEs is faster than that of the financial constrained SMEs. This means that the financial unconstrained firms with high accessibility to capital market can adjust dividend payment faster than the financial constrained firms, on the ground of their financing ability of investment funds through the market accessibility. Futhermore, the other additional results show that dividend adjustment speed of the innovative SMEs classified by the Small and Medium Business Administration is faster than that of the unclassified SMEs. They are linked with various financial policies and services such as credit guaranteed service, policy fund for SMEs, venture investment fund, insurance program, and so on. In conclusion, the past dividend per share and the current earnings per share suggested by the Lintner model explain mainly dividend adjustment speed of the innovative SMEs, and also the financial constraints explain partially. Therefore, if managers can properly understand of the relations between financial constraints and dividend smoothing of innovative SMEs, they can maintain stable and long run dividend policy of the innovative SMEs through dividend smoothing. These are encouraging results for Korea government, that is, the Small and Medium Business Administration as it has implemented many policies to commit to the innovative SMEs. This paper may have a few limitations because it may be only early study about the relations between financial constraints and dividend smoothing of the innovative SMEs. Specifically, this paper may not adequately capture all of the subtle features of the innovative SMEs and the financial unconstrained SMEs. Therefore, we think that it is necessary to expand sample firms and control variables, and use more elaborate analysis methods in the future studies.