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Commit dad42587 authored by myhloli's avatar myhloli
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Merge remote-tracking branch 'origin/master'

parents 4d6dcb00 351078f1
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317.0, 1018.0, 351.0, 91.0, 351.0], "score": 0.98, "text": "unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited."}, {"category_id": 15, "poly": [91.0, 380.0, 280.0, 380.0, 280.0, 409.0, 91.0, 409.0], "score": 0.99, "text": "Linked References"}, {"category_id": 15, "poly": [116.0, 436.0, 1515.0, 436.0, 1515.0, 468.0, 116.0, 468.0], "score": 0.97, "text": "1. 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[91.0, 205.0, 849.0, 207.0, 849.0, 241.0, 91.0, 239.0], "score": 0.98, "text": "1School of Biomedical Engineering, Capital Medical University, Beijing 100069, China"}, {"category_id": 15, "poly": [86.0, 239.0, 871.0, 241.0, 871.0, 275.0, 86.0, 273.0], "score": 0.97, "text": "2Beijing Tongren Hospital Afflated to Capital Medical University, Bejing 100730, China"}, {"category_id": 15, "poly": [89.0, 295.0, 566.0, 295.0, 566.0, 326.0, 89.0, 326.0], "score": 1.0, "text": "Received 21 December 2012; Accepted 2 June 2013"}, {"category_id": 15, "poly": [89.0, 343.0, 396.0, 346.0, 396.0, 380.0, 88.0, 378.0], "score": 1.0, "text": "Academic Editor: Wenxiang Cong"}, {"category_id": 15, "poly": [89.0, 429.0, 765.0, 429.0, 765.0, 460.0, 89.0, 460.0], "score": 0.99, "text": "and reproduction in any medium, provided the original work is properly cited."}, {"category_id": 15, "poly": [93.0, 490.0, 180.0, 490.0, 180.0, 517.0, 93.0, 517.0], "score": 1.0, "text": "Abstract"}, {"category_id": 15, "poly": [89.0, 546.0, 1500.0, 546.0, 1500.0, 577.0, 89.0, 577.0], "score": 0.98, "text": "The tilt and decentration of intraocular lens (IOL) result in defocussing, astigmatism, and wavefront aberration after operation. The objective is to give a method to"}, {"category_id": 15, "poly": [89.0, 575.0, 1518.0, 575.0, 1518.0, 607.0, 89.0, 607.0], "score": 0.97, "text": "estimate the tit and decentration ofIOL more accurately. Based on AS-OCT images of twelve eyes fromeight cases with subluxation lens afer operation, we fitted"}, {"category_id": 15, "poly": [89.0, 604.0, 1552.0, 604.0, 1552.0, 636.0, 89.0, 636.0], "score": 0.98, "text": "spherical equation to the data obtained from the images of the anterior and posterior surfaces ofthe IOL. By the established relationship between IOL tit (decentration)"}, {"category_id": 15, "poly": [89.0, 633.0, 1557.0, 633.0, 1557.0, 665.0, 89.0, 665.0], "score": 0.98, "text": "and the scanned angle, at which a piece ofAS-OCT image was taken by the instrument, the IOL tilt and decentration were calculated. IOL tilt angle and decentration of"}, {"category_id": 15, "poly": [89.0, 663.0, 1550.0, 663.0, 1550.0, 694.0, 89.0, 694.0], "score": 0.97, "text": "each subject were given. Moreover, the horizontal and vertical tit was also obtained. Accordingly, the possible errors of IOL tilt and decentration existed in the method"}, {"category_id": 15, "poly": [89.0, 692.0, 1562.0, 692.0, 1562.0, 724.0, 89.0, 724.0], "score": 0.98, "text": "employed by AS-OCT instrument. Based on 6-12 pieces of AS-OCT images at different directions, the tilt angle and decentration values were shown, respectively. The"}, {"category_id": 15, "poly": [86.0, 719.0, 1530.0, 721.0, 1530.0, 755.0, 86.0, 753.0], "score": 0.97, "text": "method ofthe surface fitting to the IOL surface can accurately analyze the IOL's location, and six pieces of AS-OCT images at three pairs symmetrical directions are"}, {"category_id": 15, "poly": [89.0, 750.0, 694.0, 750.0, 694.0, 782.0, 89.0, 782.0], "score": 0.99, "text": "enough to get tilt angle and decentration value ofIOL more precisely."}, {"category_id": 15, "poly": [91.0, 811.0, 234.0, 811.0, 234.0, 838.0, 91.0, 838.0], "score": 1.0, "text": "1. Introduction"}, {"category_id": 15, "poly": [89.0, 867.0, 1528.0, 867.0, 1528.0, 899.0, 89.0, 899.0], "score": 0.99, "text": "The operations of congenital lens subluxation have mostly implanted posterior chamber intraocular lens (IOL) through scleral suture fixation or capsular tension ring to"}, {"category_id": 15, "poly": [89.0, 897.0, 1520.0, 897.0, 1520.0, 928.0, 89.0, 928.0], "score": 0.97, "text": "combine with the capsular bag Serious IOL dislocation has been controlled, but it is dificult to avoid the tilt and decentration ofIOL [1-3]. Therefore, to obtain the"}, {"category_id": 15, "poly": [89.0, 926.0, 1446.0, 926.0, 1446.0, 960.0, 89.0, 960.0], "score": 0.98, "text": "reliable tilt and decentration of IOL could play an important role in the evaluation of the diferent operation schemes and effective treatment of postoperative"}, {"category_id": 15, "poly": [91.0, 958.0, 216.0, 958.0, 216.0, 984.0, 91.0, 984.0], "score": 0.96, "text": "complications."}, {"category_id": 15, "poly": [86.0, 1004.0, 1503.0, 1006.0, 1503.0, 1040.0, 86.0, 1038.0], "score": 0.99, "text": " Utrasound biomicroscopy (UBM), Purkinje imaging system, anterior segment optical coherence tomography (AS-OCT), and Scheimpfug imaging system are the"}, {"category_id": 15, "poly": [91.0, 1038.0, 1540.0, 1038.0, 1540.0, 1072.0, 91.0, 1072.0], "score": 0.97, "text": "methods used for measurements ofthe IOL tit and decentration in clinical practice. The Purkinje imaging system is simple, but it depends on the radius of curvature of"}, {"category_id": 15, "poly": [89.0, 1067.0, 1557.0, 1067.0, 1557.0, 1099.0, 89.0, 1099.0], "score": 0.98, "text": "the IOL surfaces. The MI image by Purkinje meter can only show parts ofthe IOL anterior and posterior surfaces. This can have an efect on the radius of curvature and"}, {"category_id": 15, "poly": [89.0, 1094.0, 1505.0, 1094.0, 1505.0, 1128.0, 89.0, 1128.0], "score": 0.97, "text": "the results of IOL tilt and decentration [4Z]. By UBM, operators can clearly see whether the IOL has tit and decentration, but the tit and decentration cannot be"}, {"category_id": 15, "poly": [89.0, 1123.0, 1545.0, 1123.0, 1545.0, 1157.0, 89.0, 1157.0], "score": 0.97, "text": "directly measured. Moreover, it is a contact inspection method and the deformation ofthe eyeballextruded by water in bath cup may affect the measured results [8. 9]."}, {"category_id": 15, "poly": [86.0, 1150.0, 1557.0, 1150.0, 1557.0, 1191.0, 86.0, 1191.0], "score": 0.86, "text": "Scheinpfug ging system can rapidly btan the IL tit and deentraton vaes, but it require pupil dlation, which can case the deviation of th pupil cente. So, th"}, {"category_id": 15, "poly": [91.0, 1182.0, 1505.0, 1182.0, 1505.0, 1216.0, 91.0, 1216.0], "score": 0.98, "text": "IOL decentration measured by the system should be a distance between the IOL center and the nonreal pupil axis, thus the resut measured is not accurate and the"}, {"category_id": 15, "poly": [89.0, 1211.0, 394.0, 1211.0, 394.0, 1243.0, 89.0, 1243.0], "score": 0.95, "text": "method has limitations [6, 10-12]."}, {"category_id": 15, "poly": [91.0, 1262.0, 1550.0, 1262.0, 1550.0, 1296.0, 91.0, 1296.0], "score": 0.99, "text": "AS-OCT is a noninvasive and noncontact imaging method of measuring the IOL tit and decentration and has been widely used in clinical practice. AS-OCT instrument "}, {"category_id": 15, "poly": [89.0, 1291.0, 1518.0, 1291.0, 1518.0, 1325.0, 89.0, 1325.0], "score": 0.97, "text": "can scan the eyeballat the rotated axis which is the ine (called a baseline) passed through the anterior cornea center and the pupil center, and a lot of images canbe"}, {"category_id": 15, "poly": [89.0, 1321.0, 1555.0, 1321.0, 1555.0, 1355.0, 89.0, 1355.0], "score": 0.98, "text": "scanned by AS-OCT at every scanned angle [13, 14]. According to each piece of scanned images, the IOL tilt and decentration are given by AS-OCT instrument. The "}, {"category_id": 15, "poly": [91.0, 1350.0, 1560.0, 1350.0, 1560.0, 1384.0, 91.0, 1384.0], "score": 0.96, "text": "maximum value ofIOL tits and decentrations obtained from al the images are taken as the IOL tlt and decentration, respectively. In clinical practice, the IOL tit degree"}, {"category_id": 15, "poly": [89.0, 1379.0, 1483.0, 1379.0, 1483.0, 1411.0, 89.0, 1411.0], "score": 0.98, "text": "is an angle between the IOL optical axis and the baseline, and the IOL decentration value is the vertical distance from the IOL center to the baseline [6, 11, 15]."}, {"category_id": 15, "poly": [89.0, 1408.0, 1525.0, 1408.0, 1525.0, 1442.0, 89.0, 1442.0], "score": 0.98, "text": "Geometrically, the IOL tit and decentration are two values independent with images. However, we have found that the IOL tit and decentration values measured on"}, {"category_id": 15, "poly": [89.0, 1438.0, 1149.0, 1438.0, 1149.0, 1472.0, 89.0, 1472.0], "score": 0.98, "text": "different images at the same scanned angle were not the same. It is possible to result in errors of IOL tit and decentration."}, {"category_id": 15, "poly": [89.0, 1489.0, 1555.0, 1489.0, 1555.0, 1520.0, 89.0, 1520.0], "score": 0.99, "text": "Due to the fact that IOL surface is similar to the spherical [6, 16], we assumed anterior and posterior surfaces ofIOL to be spherical surfaces. The equations ofthe IOL"}, {"category_id": 15, "poly": [91.0, 1518.0, 1500.0, 1518.0, 1500.0, 1552.0, 91.0, 1552.0], "score": 0.98, "text": "anterior and posterior surfaces were calculated through the AS-OCT image registration and the surface ftting method, and then the IOL tit and decentration were"}, {"category_id": 15, "poly": [91.0, 1550.0, 184.0, 1550.0, 184.0, 1576.0, 91.0, 1576.0], "score": 1.0, "text": "calculated."}, {"category_id": 15, "poly": [86.0, 1608.0, 347.0, 1608.0, 347.0, 1640.0, 86.0, 1640.0], "score": 0.98, "text": " 2. Materials and Methods"}, {"category_id": 15, "poly": [86.0, 1664.0, 261.0, 1664.0, 261.0, 1698.0, 86.0, 1698.0], "score": 0.91, "text": " 2.1. Image Obtaining"}, {"category_id": 15, "poly": [89.0, 1723.0, 1552.0, 1723.0, 1552.0, 1757.0, 89.0, 1757.0], "score": 0.97, "text": "In this study, AS-OCT images of 12 eyes of 8 patients with congenital subluxation lens were provided by the Ophthalmic Research Center of Bejing, Tongren Hospital."}, {"category_id": 15, "poly": [91.0, 1930.0, 231.0, 1930.0, 231.0, 1956.0, 91.0, 1956.0], "score": 0.98, "text": "anterior surface."}, {"category_id": 15, "poly": [89.0, 1988.0, 278.0, 1988.0, 278.0, 2013.0, 89.0, 2013.0], "score": 0.99, "text": "2.2. Image Registration"}, {"category_id": 15, "poly": [89.0, 2042.0, 1560.0, 2042.0, 1560.0, 2076.0, 89.0, 2076.0], "score": 0.97, "text": "Because the center locations of the cormeal anterior surface may be different among images, we need to use image registration for al the images from each scanned angle."}, {"category_id": 15, "poly": [84.0, 2064.0, 1545.0, 2066.0, 1545.0, 2108.0, 84.0, 2105.0], "score": 0.88, "text": "The center ofthecorneal antrior sface is regarded as arefrence pont defndbyth ntersectiopont ofcomeal antrior suface and ppendicubisetorfte"}, {"category_id": 15, "poly": [91.0, 2100.0, 1560.0, 2100.0, 1560.0, 2134.0, 91.0, 2134.0], "score": 0.99, "text": "line joining scleral spurs, which is also regarded as reference line (Figure 1). Each picture can be made rigid transformation Figure 2 gives one piece ofregistered images."}, {"category_id": 15, "poly": [86.0, 2122.0, 1501.0, 2125.0, 1500.0, 2166.0, 86.0, 2164.0], "score": 0.89, "text": "Afer image transformation, the pixel values ofthe center ofthe coreal anteror surface n mage were read t verify the corectess and validity ofthe rgid body"}, {"category_id": 15, "poly": [86.0, 2156.0, 332.0, 2159.0, 332.0, 2193.0, 86.0, 2190.0], "score": 0.98, "text": " transformation image again."}, {"category_id": 15, "poly": [1102.0, 1752.0, 1451.0, 1752.0, 1451.0, 1786.0, 1102.0, 1786.0], "score": 0.99, "text": "Moreover, it has a scan speed of2000"}, {"category_id": 15, "poly": [91.0, 1752.0, 731.0, 1752.0, 731.0, 1786.0, 91.0, 1786.0], "score": 0.98, "text": "The system takes 2000 A scans per second and has an axial resolution of"}, {"category_id": 15, "poly": [793.0, 1752.0, 1037.0, 1752.0, 1037.0, 1786.0, 793.0, 1786.0], "score": 0.95, "text": "and transverse resolution of"}, {"category_id": 15, "poly": [233.0, 1810.0, 370.0, 1810.0, 370.0, 1844.0, 233.0, 1844.0], "score": 0.95, "text": "with periods of"}, {"category_id": 15, "poly": [406.0, 1810.0, 1107.0, 1810.0, 1107.0, 1844.0, 406.0, 1844.0], "score": 0.98, "text": ", Figure 1 shows a piece of these images. Image format is RGB and image size is"}, {"category_id": 15, "poly": [89.0, 397.0, 180.0, 397.0, 180.0, 431.0, 89.0, 431.0], "score": 1.0, "text": "Copyright"}, {"category_id": 15, "poly": [205.0, 397.0, 1535.0, 397.0, 1535.0, 431.0, 205.0, 431.0], "score": 0.98, "text": "2013 Lin Liet al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution,"}, {"category_id": 15, "poly": [91.0, 1779.0, 590.0, 1779.0, 590.0, 1813.0, 91.0, 1813.0], "score": 0.98, "text": "times/second, scan time of0.125 s/row and frame rate of"}, {"category_id": 15, "poly": [649.0, 1779.0, 1532.0, 1779.0, 1532.0, 1813.0, 649.0, 1813.0], "score": 0.99, "text": "[9, 13, 14, 17]. For each eyeball the AS-OCT instrument provides 2-3 pieces of images at a degree"}, {"category_id": 15, "poly": [89.0, 1810.0, 133.0, 1810.0, 133.0, 1844.0, 89.0, 1844.0], "score": 1.0, "text": "from"}, {"category_id": 15, "poly": [160.0, 1810.0, 184.0, 1810.0, 184.0, 1844.0, 160.0, 1844.0], "score": 1.0, "text": "to"}, {"category_id": 15, "poly": [89.0, 1898.0, 966.0, 1898.0, 966.0, 1930.0, 89.0, 1930.0], "score": 0.99, "text": "Figure 1: The AS-OCT image at 30 degrees scanned angle. Points A and B are scleral spurs. Point"}, {"category_id": 15, "poly": [986.0, 1898.0, 1555.0, 1898.0, 1555.0, 1930.0, 986.0, 1930.0], "score": 0.97, "text": "is the intersection point of perpendicular bisector (L) and corneal"}], "page_info": {"page_no": 1, "height": 2339, "width": 1653}}, {"layout_dets": [{"category_id": 1, "poly": [85.54791259765625, 1992.5283203125, 1562.2015380859375, 1992.5283203125, 1562.2015380859375, 2056.579345703125, 85.54791259765625, 2056.579345703125], "score": 0.9999997019767761}, {"category_id": 1, "poly": [87.99212646484375, 1732.5474853515625, 1526.8167724609375, 1732.5474853515625, 1526.8167724609375, 1821.6837158203125, 87.99212646484375, 1821.6837158203125], "score": 0.9999996423721313}, {"category_id": 1, "poly": [87.91651916503906, 1343.5950927734375, 1564.9542236328125, 1343.5950927734375, 1564.9542236328125, 1559.619140625, 87.91651916503906, 1559.619140625], "score": 0.9999995231628418}, {"category_id": 1, "poly": [88.61979675292969, 192.71449279785156, 1564.0771484375, 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"z^{'}=y,\\!(1)"}, {"category_id": 13, "poly": [1118, 1380, 1135, 1380, 1135, 1402, 1118, 1402], "score": 0.62, "latex": "F"}, {"category_id": 13, "poly": [304, 590, 320, 590, 320, 611, 304, 611], "score": 0.61, "latex": "\\gamma"}, {"category_id": 13, "poly": [1011, 1500, 1045, 1500, 1045, 1524, 1011, 1524], "score": 0.59, "latex": "E F"}, {"category_id": 13, "poly": [680, 1472, 695, 1472, 695, 1494, 680, 1494], "score": 0.58, "latex": "d"}, {"category_id": 14, "poly": [429, 864, 851, 864, 851, 941, 429, 941], "score": 0.58, "latex": "d=\\sqrt{d_{1}^{2}+\\left[\\left(\\frac{b_{2}-b_{1}}{a_{2}-a_{1}}\\right)d_{1}+\\frac{a_{2}b_{1}-a_{1}b_{2}}{a_{2}-a_{1}}\\right]^{2}},"}, {"category_id": 13, "poly": [1145, 255, 1166, 255, 1166, 277, 1145, 277], "score": 0.54, "latex": "Z"}, {"category_id": 13, "poly": [88, 254, 111, 254, 111, 278, 88, 278], "score": 0.54, "latex": "X"}, {"category_id": 13, "poly": [783, 1408, 878, 1408, 878, 1433, 783, 1433], "score": 0.52, "latex": "E F\\perp O E"}, {"category_id": 13, "poly": [370, 1529, 385, 1529, 385, 1552, 370, 1552], "score": 0.5, "latex": "d"}, {"category_id": 13, "poly": [1303, 1433, 1389, 1433, 1389, 1464, 1303, 1464], "score": 0.5, "latex": "\\dot{\\bf\\Phi}(\\alpha-\\rho)\\,d"}, {"category_id": 13, "poly": [1181, 1433, 1511, 1433, 1511, 1465, 1181, 1465], "score": 0.43, "latex": "d_{2}\\left(\\alpha\\right)=\\cos{\\stackrel{\\bullet}{\\left(\\alpha-\\rho\\right)}}\\,d.(5)\\;\\mathrm{{The\\;IOL}}"}, {"category_id": 13, "poly": [466, 324, 580, 324, 580, 345, 466, 345], "score": 0.43, "latex": "x\\ =x\\cos\\alpha"}, {"category_id": 13, "poly": [466, 313, 874, 313, 874, 348, 466, 348], "score": 0.43, "latex": "x^{'}=x\\cos\\alpha,~~~~~y^{'}=x\\sin\\alpha,~~~~~z^{'}=y,\\bar{(1)}"}, {"category_id": 13, "poly": [1101, 1350, 1147, 1350, 1147, 1377, 1101, 1377], "score": 0.42, "latex": "\\mathrm{{TOL},}"}, {"category_id": 13, "poly": [1024, 1380, 1071, 1380, 1071, 1405, 1024, 1405], "score": 0.41, "latex": "O,E"}, {"category_id": 13, "poly": [406, 1408, 422, 1408, 422, 1432, 406, 1432], "score": 0.38, "latex": "d"}, {"category_id": 13, "poly": [1238, 1471, 1255, 1471, 1255, 1494, 1238, 1494], "score": 0.36, "latex": "d"}, {"category_id": 13, "poly": [621, 317, 735, 317, 735, 348, 621, 348], "score": 0.35, "latex": "y^{'}=x\\sin\\alpha"}, {"category_id": 13, "poly": [240, 1244, 254, 1244, 254, 1263, 240, 1263], "score": 0.34, "latex": "\\cdot_{\\alpha}"}, {"category_id": 13, "poly": [149, 1997, 166, 1997, 166, 2022, 149, 2022], "score": 0.29, "latex": "\\underline{{6}}"}, {"category_id": 13, "poly": [88, 1299, 104, 1299, 104, 1323, 88, 1323], "score": 0.28, "latex": "\\theta"}, {"category_id": 13, "poly": [798, 255, 819, 255, 819, 277, 798, 277], "score": 0.27, "latex": "Y"}, {"category_id": 13, "poly": [1054, 1381, 1072, 1381, 1072, 1403, 1054, 1403], "score": 0.26, "latex": "E"}, {"category_id": 15, "poly": [89.0, 139.0, 354.0, 139.0, 354.0, 171.0, 89.0, 171.0], "score": 1.0, "text": "2.3. Collecting IOL Surface Data"}, {"category_id": 15, "poly": [89.0, 197.0, 1557.0, 197.0, 1557.0, 229.0, 89.0, 229.0], "score": 0.99, "text": "From each piece of AS-OCT images, we can obtain two-dimensional pixel coordinates of points of the IOL anterior and posterior surfaces. In order to obtain the three-"}, {"category_id": 15, "poly": [89.0, 227.0, 1557.0, 227.0, 1557.0, 261.0, 89.0, 261.0], "score": 0.98, "text": "dimensional coordinates of points of the IOL surface data, Cartesian coordinate system is needed. We set the horizontal direction (alar to zygomatic direction) parallel to"}, {"category_id": 15, "poly": [91.0, 329.0, 428.0, 329.0, 428.0, 361.0, 91.0, 361.0], "score": 0.98, "text": "relations between them are as follows:"}, {"category_id": 15, "poly": [91.0, 387.0, 642.0, 387.0, 642.0, 412.0, 91.0, 412.0], "score": 0.97, "text": "2.4.TheTilt and Decentration of IOL Calculated by GeometricMethod"}, {"category_id": 15, "poly": [686.0, 670.0, 713.0, 670.0, 713.0, 692.0, 686.0, 692.0], "score": 0.75, "text": "(2)"}, {"category_id": 15, "poly": [91.0, 816.0, 654.0, 816.0, 654.0, 848.0, 91.0, 848.0], "score": 0.98, "text": "Figure 3: The geometrical definition of IOL tilt and decentration"}, {"category_id": 15, "poly": [849.0, 936.0, 883.0, 936.0, 883.0, 965.0, 849.0, 965.0], "score": 0.98, "text": "(3)"}, {"category_id": 15, "poly": [89.0, 1014.0, 403.0, 1014.0, 403.0, 1045.0, 89.0, 1045.0], "score": 0.99, "text": "Decentration equation is as follows:"}, {"category_id": 15, "poly": [86.0, 1099.0, 571.0, 1101.0, 571.0, 1133.0, 86.0, 1130.0], "score": 0.97, "text": " 2.5. IOL Tilt Calculated When the Different Scanned Angles"}, {"category_id": 15, "poly": [89.0, 1157.0, 1557.0, 1157.0, 1557.0, 1189.0, 89.0, 1189.0], "score": 0.98, "text": "The IOL tilt and decentration at different scanned angles were calculated based on the equations ofthe IOL anterior and posterior surface. For the AS-OCT image with"}, {"category_id": 15, "poly": [1390.0, 1245.0, 1525.0, 1245.0, 1525.0, 1272.0, 1390.0, 1272.0], "score": 0.95, "text": "Apparently, as"}, {"category_id": 15, "poly": [86.0, 1615.0, 831.0, 1618.0, 831.0, 1652.0, 86.0, 1649.0], "score": 0.98, "text": " Figure 4: The projection of IOL center point in the plane at different scanned angles."}, {"category_id": 15, "poly": [89.0, 1679.0, 192.0, 1679.0, 192.0, 1706.0, 89.0, 1706.0], "score": 0.99, "text": "3. Results"}, {"category_id": 15, "poly": [89.0, 1737.0, 1520.0, 1737.0, 1520.0, 1771.0, 89.0, 1771.0], "score": 0.96, "text": "Figure 5 shows the IOL ftting surface of case 11. Table 1 gives the IOL tilt and decentration calculated by the surface fitting approach and their values given by AS-"}, {"category_id": 15, "poly": [89.0, 1796.0, 723.0, 1796.0, 723.0, 1827.0, 89.0, 1827.0], "score": 0.99, "text": "shown in the ninth-tenth colum of Table 1, was between 0.85 and 0.97."}, {"category_id": 15, "poly": [89.0, 1878.0, 792.0, 1881.0, 792.0, 1915.0, 89.0, 1913.0], "score": 0.97, "text": "Table 1: The IOL tilt and decentration obtained by the method of surface ftting."}, {"category_id": 15, "poly": [91.0, 1947.0, 1001.0, 1947.0, 1001.0, 1978.0, 91.0, 1978.0], "score": 0.98, "text": "Figure 5: The image of IOL fiting surface and intersection of the anterior and posterior surfaces of IOL."}, {"category_id": 15, "poly": [89.0, 2030.0, 1471.0, 2030.0, 1471.0, 2061.0, 89.0, 2061.0], "score": 0.96, "text": "respect to the change of scanned angle. But the data provided by As-OCT instrument oscillates with a small amplitude. It definitely affects the estimation of tlt."}, {"category_id": 15, "poly": [91.0, 2115.0, 986.0, 2115.0, 986.0, 2147.0, 91.0, 2147.0], "score": 0.98, "text": "Figure 6: The relation with IOL tits by the method of surface fitting and AS-OCT and scanned angles."}, {"category_id": 15, "poly": [89.0, 2166.0, 1525.0, 2166.0, 1525.0, 2198.0, 89.0, 2198.0], "score": 0.98, "text": "Figure 7 gives data of the decentration calculated by the method of surface fitting and provided by AS-OCT instrument for case 12. It is shown that the trend oftwo"}, {"category_id": 15, "poly": [91.0, 2195.0, 1550.0, 2195.0, 1550.0, 2227.0, 91.0, 2227.0], "score": 0.97, "text": "curves is inconsistent with respect to the change of scanned angle. But the data provided by AS-OCT instrument oscillates with a large amplitude. According to formula"}, {"category_id": 15, "poly": [992.0, 1442.0, 1154.0, 1442.0, 1154.0, 1476.0, 992.0, 1476.0], "score": 0.97, "text": ", can be obtained"}, {"category_id": 15, "poly": [91.0, 2224.0, 271.0, 2224.0, 271.0, 2259.0, 91.0, 2259.0], "score": 0.99, "text": "(5), the decentration"}, {"category_id": 15, "poly": [328.0, 2224.0, 1080.0, 2224.0, 1080.0, 2259.0, 328.0, 2259.0], "score": 0.98, "text": " changes in accordance with cosine approximately. Clearly, the change of decentration"}, {"category_id": 15, "poly": [1137.0, 2224.0, 1555.0, 2224.0, 1555.0, 2259.0, 1137.0, 2259.0], "score": 0.97, "text": "calculated by our method is in accordance with"}, {"category_id": 15, "poly": [1021.0, 1269.0, 1557.0, 1267.0, 1557.0, 1301.0, 1021.0, 1304.0], "score": 0.97, "text": "is a maxima, which is exactly equal to tit. Therefore, the tilt ("}, {"category_id": 15, "poly": [697.0, 1269.0, 963.0, 1267.0, 963.0, 1301.0, 697.0, 1304.0], "score": 0.97, "text": "attains its minimum value, and"}, {"category_id": 15, "poly": [89.0, 1498.0, 201.0, 1501.0, 201.0, 1535.0, 89.0, 1533.0], "score": 0.98, "text": "decentration"}, {"category_id": 15, "poly": [91.0, 1472.0, 201.0, 1472.0, 201.0, 1506.0, 91.0, 1506.0], "score": 1.0, "text": "decentration"}, {"category_id": 15, "poly": [89.0, 290.0, 942.0, 290.0, 942.0, 322.0, 89.0, 322.0], "score": 0.99, "text": "surface is as the origin of coordinates. Assuming that the two-dimensional coordinate of point A is"}, {"category_id": 15, "poly": [999.0, 290.0, 1493.0, 290.0, 1493.0, 322.0, 999.0, 322.0], "score": 0.97, "text": ", and the three-dimensional coordinate is (x y ,z \uff09, the"}, {"category_id": 15, "poly": [451.0, 1269.0, 467.0, 1267.0, 467.0, 1301.0, 451.0, 1304.0], "score": 0.77, "text": "\uff0c"}, {"category_id": 15, "poly": [1203.0, 1408.0, 1476.0, 1406.0, 1476.0, 1440.0, 1203.0, 1442.0], "score": 0.95, "text": ", and the equation of line OE is"}, {"category_id": 15, "poly": [631.0, 1243.0, 809.0, 1243.0, 809.0, 1274.0, 631.0, 1274.0], "score": 0.98, "text": ", from the following:"}, {"category_id": 15, "poly": [706.0, 1043.0, 826.0, 1043.0, 826.0, 1077.0, 706.0, 1077.0], "score": 0.96, "text": ", respectively."}, {"category_id": 15, "poly": [434.0, 1998.0, 1560.0, 1998.0, 1560.0, 2032.0, 434.0, 2032.0], "score": 0.97, "text": " defined by formula (4) and provided by AS-OCT instrument for case 12. It is found that the trend oftwo curves is identical with"}, {"category_id": 15, "poly": [91.0, 443.0, 918.0, 443.0, 918.0, 475.0, 91.0, 475.0], "score": 0.97, "text": "From Figure 3, 0, known as tilt of IOL, is an angle between visual axis and optical axis of IOL."}, {"category_id": 15, "poly": [938.0, 443.0, 1535.0, 443.0, 1535.0, 475.0, 938.0, 475.0], "score": 0.97, "text": ", defined as tit at the horizontal direction, is an angle between optical"}, {"category_id": 15, "poly": [89.0, 1043.0, 620.0, 1043.0, 620.0, 1077.0, 89.0, 1077.0], "score": 0.98, "text": "ofthe fied IOL anterior and posterior surface with radius of"}, {"category_id": 15, "poly": [645.0, 1043.0, 683.0, 1043.0, 683.0, 1077.0, 645.0, 1077.0], "score": 1.0, "text": "and"}, {"category_id": 15, "poly": [1082.0, 1408.0, 1093.0, 1406.0, 1093.0, 1440.0, 1082.0, 1442.0], "score": 0.7, "text": "\uff0c"}, {"category_id": 15, "poly": [950.0, 314.0, 1215.0, 322.0, 1215.0, 363.0, 950.0, 356.0], "score": 0.95, "text": "is scanned angle of AS-OCT."}, {"category_id": 15, "poly": [84.0, 1759.0, 1480.0, 1762.0, 1480.0, 1803.0, 84.0, 1801.0], "score": 0.94, "text": "OCT instrument. The eighth coummn of Table 1 gives the diameter ofIOL computed by the method of surface fiting The goodness-oft (corelation coeficient"}, {"category_id": 15, "poly": [1510.0, 1759.0, 1525.0, 1762.0, 1525.0, 1803.0, 1510.0, 1801.0], "score": 0.73, "text": "\uff0c"}, {"category_id": 15, "poly": [259.0, 1498.0, 876.0, 1501.0, 876.0, 1535.0, 259.0, 1533.0], "score": 0.97, "text": "calculated from all of different scanmned angle images. If there is a tit of"}, {"category_id": 15, "poly": [202.0, 1442.0, 935.0, 1442.0, 935.0, 1476.0, 202.0, 1476.0], "score": 0.97, "text": ", for the AS-OCT image with scanned angle of \u03b1, the IOL decentration, denoted by"}, {"category_id": 15, "poly": [89.0, 1352.0, 723.0, 1352.0, 723.0, 1386.0, 89.0, 1386.0], "score": 0.99, "text": "For a piece of AS-OCT image with scanned angle of\u03b1 (Figure 4), point"}, {"category_id": 15, "poly": [89.0, 587.0, 232.0, 587.0, 232.0, 621.0, 89.0, 621.0], "score": 0.97, "text": "axis ofIOL and"}, {"category_id": 15, "poly": [89.0, 1381.0, 578.0, 1381.0, 578.0, 1413.0, 89.0, 1413.0], "score": 0.99, "text": "center ofIOL on XOY plane (coordinate plane, Figure"}, {"category_id": 15, "poly": [871.0, 314.0, 932.0, 322.0, 932.0, 363.0, 871.0, 356.0], "score": 0.99, "text": "where"}, {"category_id": 15, "poly": [1136.0, 1381.0, 1550.0, 1381.0, 1550.0, 1413.0, 1136.0, 1413.0], "score": 0.97, "text": "were the same one. The length of segment OF"}, {"category_id": 15, "poly": [254.0, 587.0, 303.0, 587.0, 303.0, 621.0, 254.0, 621.0], "score": 0.94, "text": "-axis."}, {"category_id": 15, "poly": [321.0, 587.0, 1316.0, 587.0, 1316.0, 621.0, 321.0, 621.0], "score": 0.97, "text": ". defined as tit at vertical direction, is an angle between optical axis ofIOL and Y axis, and we know the folowing"}, {"category_id": 15, "poly": [924.0, 1498.0, 1010.0, 1501.0, 1010.0, 1535.0, 924.0, 1533.0], "score": 1.0, "text": "segments"}, {"category_id": 15, "poly": [1046.0, 1498.0, 1505.0, 1501.0, 1505.0, 1535.0, 1046.0, 1533.0], "score": 0.97, "text": "and OE are nearly orthogonal; then the maximum of"}, {"category_id": 15, "poly": [259.0, 1472.0, 679.0, 1472.0, 679.0, 1506.0, 259.0, 1506.0], "score": 0.96, "text": "attains is maximum value, the IOL decentration"}, {"category_id": 15, "poly": [696.0, 1472.0, 833.0, 1472.0, 833.0, 1506.0, 696.0, 1506.0], "score": 1.0, "text": ", as long as cos"}, {"category_id": 15, "poly": [1167.0, 256.0, 1510.0, 256.0, 1510.0, 288.0, 1167.0, 288.0], "score": 0.98, "text": "axis. The center ofthe corneal anterior"}, {"category_id": 15, "poly": [879.0, 1408.0, 971.0, 1406.0, 971.0, 1440.0, 879.0, 1442.0], "score": 0.96, "text": ". Defining."}, {"category_id": 15, "poly": [89.0, 1530.0, 369.0, 1530.0, 369.0, 1562.0, 89.0, 1562.0], "score": 1.0, "text": "is close to the IOL decentration"}, {"category_id": 15, "poly": [1390.0, 1430.0, 1511.0, 1435.0, 1510.0, 1477.0, 1390.0, 1471.0], "score": 1.0, "text": "(5) The IOL"}, {"category_id": 15, "poly": [743.0, 1352.0, 1100.0, 1352.0, 1100.0, 1386.0, 743.0, 1386.0], "score": 0.97, "text": "is the projection point of image center of"}, {"category_id": 15, "poly": [1148.0, 1352.0, 1515.0, 1352.0, 1515.0, 1386.0, 1148.0, 1386.0], "score": 0.97, "text": " and point F is the projection point of real"}, {"category_id": 15, "poly": [600.0, 1381.0, 1023.0, 1381.0, 1023.0, 1413.0, 600.0, 1413.0], "score": 0.98, "text": ". Ifthere were not any decentration, three points"}, {"category_id": 15, "poly": [86.0, 1408.0, 405.0, 1406.0, 405.0, 1440.0, 86.0, 1442.0], "score": 0.98, "text": "is the IOL decentration, denoted by"}, {"category_id": 15, "poly": [423.0, 1408.0, 782.0, 1406.0, 782.0, 1440.0, 423.0, 1442.0], "score": 0.95, "text": ". Ifthere were not any IOL tilt, we know"}, {"category_id": 15, "poly": [944.0, 1472.0, 1237.0, 1472.0, 1237.0, 1506.0, 944.0, 1506.0], "score": 0.97, "text": ". Therefore, the IOL decentration"}, {"category_id": 15, "poly": [1256.0, 1472.0, 1473.0, 1472.0, 1473.0, 1506.0, 1256.0, 1506.0], "score": 0.99, "text": "is the maximum value of"}, {"category_id": 15, "poly": [91.0, 1243.0, 239.0, 1243.0, 239.0, 1274.0, 91.0, 1274.0], "score": 0.99, "text": "scanned angle of"}, {"category_id": 15, "poly": [255.0, 1243.0, 581.0, 1243.0, 581.0, 1274.0, 255.0, 1274.0], "score": 0.96, "text": ", one can get the IOL tilt, denoted by"}, {"category_id": 15, "poly": [91.0, 1998.0, 148.0, 1998.0, 148.0, 2032.0, 91.0, 2032.0], "score": 1.0, "text": "Figure"}, {"category_id": 15, "poly": [167.0, 1998.0, 383.0, 1998.0, 383.0, 2032.0, 167.0, 2032.0], "score": 0.93, "text": "gives the graph of the tilt"}, {"category_id": 15, "poly": [105.0, 1301.0, 863.0, 1301.0, 863.0, 1333.0, 105.0, 1333.0], "score": 0.96, "text": ") should take the maximum value from the tits calculated at the different scanned angles."}, {"category_id": 15, "poly": [112.0, 256.0, 797.0, 256.0, 797.0, 288.0, 112.0, 288.0], "score": 0.99, "text": "axis, the vertical direction (nasal bone to the jaw bone direction) parallel to the"}, {"category_id": 15, "poly": [820.0, 256.0, 1144.0, 256.0, 1144.0, 288.0, 820.0, 288.0], "score": 0.99, "text": "axis, and the ocular axial is set as the"}, {"category_id": 15, "poly": [1073.0, 1381.0, 1117.0, 1381.0, 1117.0, 1413.0, 1073.0, 1413.0], "score": 0.9, "text": ", and"}], "page_info": {"page_no": 2, "height": 2339, "width": 1653}}, {"layout_dets": [{"category_id": 1, "poly": [92.0838623046875, 1900.6451416015625, 559.0983276367188, 1900.6451416015625, 559.0983276367188, 1928.751220703125, 92.0838623046875, 1928.751220703125], "score": 0.9999998807907104}, {"category_id": 1, "poly": [91.62836456298828, 851.543701171875, 1564.9864501953125, 851.543701171875, 1564.9864501953125, 967.3631591796875, 91.62836456298828, 967.3631591796875], "score": 0.9999996423721313}, {"category_id": 1, "poly": [92.05652618408203, 215.79888916015625, 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200.0], "score": 0.98, "text": "Figure 7: The relation with IOL decentration by the method of surface fitting and AS-OCT and scanned angles."}, {"category_id": 15, "poly": [91.0, 219.0, 1562.0, 219.0, 1562.0, 253.0, 91.0, 253.0], "score": 0.97, "text": "Table 2 gives the results ofthe IOL tilt and decentration of three cases by two methods in different scanned angles (The \u201c' shown in the Table 2 means that this data is"}, {"category_id": 15, "poly": [91.0, 249.0, 1528.0, 249.0, 1528.0, 283.0, 91.0, 283.0], "score": 0.97, "text": "not available). The resuts ofIOL tit and decentration shown in Table 3 were calculated by surface ftting method based on 6, 7, 8, 9, 10, and 11 pieces ofAS-OCT"}, {"category_id": 15, "poly": [91.0, 283.0, 268.0, 283.0, 268.0, 309.0, 91.0, 309.0], "score": 0.94, "text": "images, respectively."}, {"category_id": 15, "poly": [89.0, 363.0, 861.0, 366.0, 861.0, 400.0, 89.0, 397.0], "score": 0.97, "text": "Table 2: IOL decentration and tit obtained from the image with different scanned angle."}, {"category_id": 15, "poly": [89.0, 426.0, 1225.0, 429.0, 1225.0, 463.0, 89.0, 460.0], "score": 0.97, "text": "Table 3: IOL tilt and decentration calculated by surface ftting method based on 6, 7, 8, 9, 10, and 11 pieces of AS-OCT images."}, {"category_id": 15, "poly": [87.0, 482.0, 224.0, 488.0, 223.0, 522.0, 86.0, 516.0], "score": 1.0, "text": "4. Discussion"}, {"category_id": 15, "poly": [89.0, 541.0, 1508.0, 543.0, 1508.0, 585.0, 89.0, 582.0], "score": 0.77, "text": "According tCes, tILtitadderation we calculatd bycolletingdatafI sface and shercal fting to te dta ofIL aeror ad"}, {"category_id": 15, "poly": [91.0, 629.0, 1503.0, 629.0, 1503.0, 663.0, 91.0, 663.0], "score": 0.97, "text": "Korynta et al [18] showed that the drif and oblique astigmatism can be caused by the IOL decentration being more than 1 mm and the IOL tit being more than 5"}, {"category_id": 15, "poly": [86.0, 653.0, 1547.0, 653.0, 1547.0, 694.0, 86.0, 694.0], "score": 0.89, "text": "degres Inour results, the decentration ofone ee was greater than mmand the tits of3 eyes were greater than 5 degrees. The IL tit and decentrationfthe othr"}, {"category_id": 15, "poly": [89.0, 687.0, 1540.0, 687.0, 1540.0, 721.0, 89.0, 721.0], "score": 0.96, "text": "8 eyes basically were within the normal range given by Korynta. It is noticed that most ofthe cases used in this study are successful in operations. This verified that our"}, {"category_id": 15, "poly": [89.0, 746.0, 1537.0, 746.0, 1537.0, 780.0, 89.0, 780.0], "score": 0.98, "text": "optical diameter obtained in this study was basicall in this range (Table 1). We noticed that the calculated IOL diameters are slightly larger than those provided by the"}, {"category_id": 15, "poly": [89.0, 775.0, 1535.0, 772.0, 1535.0, 806.0, 89.0, 809.0], "score": 0.97, "text": "manufacturer. The reason is that the edge ofIOL was made with a smooth and certain thickness shape, but we have not taken into account this issue in the calculation"}, {"category_id": 15, "poly": [86.0, 804.0, 187.0, 804.0, 187.0, 838.0, 86.0, 838.0], "score": 0.97, "text": "(Figure Z)."}, {"category_id": 15, "poly": [91.0, 855.0, 1469.0, 855.0, 1469.0, 887.0, 91.0, 887.0], "score": 0.97, "text": "The results oftilt calculated by surface ftting (Table 1, 1.76-7.52 degrees) were higher than those of Dhivya's study (0.04-3.6 degrees) [19]. Besides sample"}, {"category_id": 15, "poly": [91.0, 884.0, 1562.0, 884.0, 1562.0, 919.0, 91.0, 919.0], "score": 0.97, "text": "differences, the main reason is that the maximum value obtained from the four images (0 degrees, 90 degrees, 45 degrees, and 135 degrees [19]) is possibly less than the"}, {"category_id": 15, "poly": [86.0, 1138.0, 1523.0, 1138.0, 1523.0, 1179.0, 86.0, 1179.0], "score": 0.92, "text": "elninated byregistrationof images at diferent scanned directions and selecting as many as possibl pixel ponts to a certan extent So, the IL tit and decentration"}, {"category_id": 15, "poly": [86.0, 1167.0, 586.0, 1170.0, 585.0, 1204.0, 86.0, 1201.0], "score": 0.97, "text": " calculated with the method of surface fitting are accurate."}, {"category_id": 15, "poly": [89.0, 1221.0, 1540.0, 1221.0, 1540.0, 1255.0, 89.0, 1255.0], "score": 0.97, "text": "In order to reduce the pressure ofclinical work, it is very significant to provide the method for calculating the more accurate tilt and decentration ofIOL and saving the"}, {"category_id": 15, "poly": [91.0, 1250.0, 1545.0, 1250.0, 1545.0, 1284.0, 91.0, 1284.0], "score": 0.98, "text": "workload. Table 3 gives the results of IOL tilt and decentration calculated with 11, 10, 9, 8, 7, 6 AS-OCT images, respectively by the method. This problem is one of"}, {"category_id": 15, "poly": [89.0, 1279.0, 1557.0, 1279.0, 1557.0, 1313.0, 89.0, 1313.0], "score": 0.98, "text": "innovations of this study. Although the number of images used to obtain IOL tilt and decentration are 2 (90 degrees and 180 degrees) [6, 15], 4 (0 degrees, 45 degrees,"}, {"category_id": 15, "poly": [89.0, 1367.0, 1427.0, 1367.0, 1427.0, 1401.0, 89.0, 1401.0], "score": 0.98, "text": "practice. It is suggested that the method can calculate the more accurate tit and decentration of IOL with scanned angles at the six symmetrical directions."}, {"category_id": 15, "poly": [89.0, 1418.0, 1555.0, 1418.0, 1555.0, 1452.0, 89.0, 1452.0], "score": 0.98, "text": "The IOL tit measured by AS-COT instrument is the angle between the IOL optical axis and the ine joining the centers ofthe anterior cornea and the pupil Our method"}, {"category_id": 15, "poly": [91.0, 1447.0, 1518.0, 1447.0, 1518.0, 1481.0, 91.0, 1481.0], "score": 0.95, "text": "can not only give the IOL tilt, but aso the tilt at the horizontal direction and the tit at the verticaldirection To the knowldge ofthe authors, it has not been reported"}, {"category_id": 15, "poly": [91.0, 1476.0, 1528.0, 1476.0, 1528.0, 1511.0, 91.0, 1511.0], "score": 0.97, "text": "whether the horizontal and vertical angles can affect the recovery of vision and optical imaging quality. This may be related to the current methods in clinic leaving two"}, {"category_id": 15, "poly": [89.0, 1506.0, 1409.0, 1506.0, 1409.0, 1540.0, 89.0, 1540.0], "score": 0.97, "text": "angles unknown. Therefore, it should be studied that whether the horizontal and vertical angles have an impact on visual acuity and visual efect in future."}, {"category_id": 15, "poly": [91.0, 1557.0, 1537.0, 1557.0, 1537.0, 1591.0, 91.0, 1591.0], "score": 0.97, "text": "This study is limited in the follwing: because IOL was covered by ris and opaque tissues, the middle part ofIOL is only displayed in the image, and the point near the"}, {"category_id": 15, "poly": [91.0, 1586.0, 1532.0, 1586.0, 1532.0, 1618.0, 91.0, 1618.0], "score": 0.97, "text": "IOL boundary cannot be obtained. In addition, artificial selection and obtaining pixel coordinates will bring the errors. This will affect the similarity ofthe fitting surface"}, {"category_id": 15, "poly": [91.0, 1615.0, 1532.0, 1615.0, 1532.0, 1649.0, 91.0, 1649.0], "score": 0.96, "text": "and the actual IOL surface. Therefore, it should be studied that the method can reduce errors in collcting data for improving the ftting goodness in future. In addiion,"}, {"category_id": 15, "poly": [89.0, 1645.0, 1513.0, 1645.0, 1513.0, 1679.0, 89.0, 1679.0], "score": 0.96, "text": "this study assumed that the IOL surface was spherical. But the aspheric surface cannot be thought about. It is hoped that the IOL suface can be calculated with the"}, {"category_id": 15, "poly": [89.0, 1674.0, 1564.0, 1674.0, 1564.0, 1708.0, 89.0, 1708.0], "score": 0.98, "text": "method of aspheric ftting in future. Moreover, compared with two methods of spherical and aspheric ftting, the results calculated with two methods can be more close to"}, {"category_id": 15, "poly": [89.0, 1703.0, 305.0, 1703.0, 305.0, 1735.0, 89.0, 1735.0], "score": 0.99, "text": "the real values in clinical"}, {"category_id": 15, "poly": [89.0, 1752.0, 1555.0, 1754.0, 1555.0, 1788.0, 89.0, 1786.0], "score": 0.97, "text": "In conclusion, the method ofthe surface ftting to the IOL surface can accurately analyze the IOL's location, and six piece of AS-OCT images at three pairs symmetrical"}, {"category_id": 15, "poly": [89.0, 1786.0, 814.0, 1786.0, 814.0, 1818.0, 89.0, 1818.0], "score": 0.97, "text": "directions are enough to get ilt angle and decentration value of IOL more precisely."}, {"category_id": 15, "poly": [91.0, 1844.0, 307.0, 1844.0, 307.0, 1876.0, 91.0, 1876.0], "score": 0.98, "text": "Authors\u2019 Contribution"}, {"category_id": 15, "poly": [89.0, 1903.0, 558.0, 1903.0, 558.0, 1935.0, 89.0, 1935.0], "score": 0.99, "text": "Lin Li and Ke Wang contributed equally to this work."}, {"category_id": 15, "poly": [93.0, 1966.0, 266.0, 1966.0, 266.0, 1993.0, 93.0, 1993.0], "score": 0.92, "text": "Acknowle dgme nts"}, {"category_id": 15, "poly": [91.0, 2020.0, 1520.0, 2020.0, 1520.0, 2054.0, 91.0, 2054.0], "score": 0.98, "text": "This work was financially supported by the National Natural Science Foundation ofChina (no. 31070840), the Beijing Natural Science Foundation (3122010), and"}, {"category_id": 15, "poly": [89.0, 2051.0, 1038.0, 2051.0, 1038.0, 2083.0, 89.0, 2083.0], "score": 0.98, "text": "Bejing Leading Academic Discipline Project of Bejing Municipal education Commission (PHR201110506)."}, {"category_id": 15, "poly": [87.0, 2105.0, 207.0, 2110.0, 205.0, 2145.0, 86.0, 2139.0], "score": 1.0, "text": "References"}, {"category_id": 15, "poly": [116.0, 2168.0, 1520.0, 2168.0, 1520.0, 2203.0, 116.0, 2203.0], "score": 0.96, "text": "1. M. Scherer, E. Bertelmann, and P. Rieck, \u201cLate spontaneous in-the-bag intraocular ens and capsular tension ring dislocation in pseudoexfoliation syndrome,\u201d\""}, {"category_id": 15, "poly": [145.0, 2198.0, 1427.0, 2198.0, 1427.0, 2232.0, 145.0, 2232.0], "score": 0.98, "text": "Journal of Cataract and Refractive Surgery, vol. 32, no. 4, pp. 672-675, 2006. View at Publisher \u00b7 View at Google Scholar View at Scopus"}, {"category_id": 15, "poly": [113.0, 2227.0, 1545.0, 2227.0, 1545.0, 2261.0, 113.0, 2261.0], "score": 0.98, "text": "2. H. Saedon, W. H. Chan, and R. Radford, \u201cAnterior dislocation ofa Morcher capsular tension ring\" Journal of Cataract and Refractive Surgery, vol. 37, no."}, {"category_id": 15, "poly": [1387.0, 994.0, 1550.0, 994.0, 1550.0, 1028.0, 1387.0, 1028.0], "score": 1.0, "text": "when the scanned"}, {"category_id": 15, "poly": [630.0, 1111.0, 1481.0, 1111.0, 1481.0, 1145.0, 630.0, 1145.0], "score": 0.98, "text": "calculated from each image could cause larger accumulation errors. In our method, the errors are"}, {"category_id": 15, "poly": [1436.0, 1053.0, 1552.0, 1053.0, 1552.0, 1087.0, 1436.0, 1087.0], "score": 0.97, "text": "among of all"}, {"category_id": 15, "poly": [91.0, 994.0, 857.0, 994.0, 857.0, 1028.0, 91.0, 1028.0], "score": 0.99, "text": "Assume that IOL anterior and posterior surfaces are spheres. We give the formula oftilt"}, {"category_id": 15, "poly": [908.0, 994.0, 1329.0, 994.0, 1329.0, 1028.0, 908.0, 1028.0], "score": 0.99, "text": " and the approximate expression of decentration"}, {"category_id": 15, "poly": [89.0, 1053.0, 113.0, 1053.0, 113.0, 1087.0, 89.0, 1087.0], "score": 1.0, "text": "tit"}, {"category_id": 15, "poly": [164.0, 1053.0, 317.0, 1053.0, 317.0, 1087.0, 164.0, 1087.0], "score": 0.96, "text": " and decentration"}, {"category_id": 15, "poly": [89.0, 1111.0, 369.0, 1111.0, 369.0, 1145.0, 89.0, 1145.0], "score": 0.98, "text": "errors are not eliminated, the tit"}, {"category_id": 15, "poly": [420.0, 1111.0, 573.0, 1111.0, 573.0, 1145.0, 420.0, 1145.0], "score": 0.97, "text": " and decentration"}, {"category_id": 15, "poly": [91.0, 914.0, 724.0, 914.0, 724.0, 948.0, 91.0, 948.0], "score": 0.96, "text": "IOL tilt (see, (4). Our results are consistent with those of Xue et al. (tilt,"}, {"category_id": 15, "poly": [89.0, 716.0, 1311.0, 711.0, 1311.0, 746.0, 89.0, 750.0], "score": 0.96, "text": "results were in accordance with results of the literatures and clinical In addition, optical diameter of the IOL provided by the manufacturer is"}, {"category_id": 15, "poly": [1445.0, 716.0, 1532.0, 711.0, 1533.0, 746.0, 1445.0, 750.0], "score": 1.0, "text": "The IOL"}, {"category_id": 15, "poly": [89.0, 943.0, 280.0, 943.0, 280.0, 977.0, 89.0, 977.0], "score": 1.0, "text": "degrees; decentration"}, {"category_id": 15, "poly": [456.0, 943.0, 1560.0, 943.0, 1560.0, 977.0, 456.0, 977.0], "score": 0.99, "text": "[21]. In fact, the IOL tit and decentration were possibly involved in the difference of individuals, surgeons, and measurements."}, {"category_id": 15, "poly": [835.0, 914.0, 1030.0, 914.0, 1030.0, 948.0, 835.0, 948.0], "score": 0.96, "text": "degrees; decentration"}, {"category_id": 15, "poly": [1182.0, 914.0, 1557.0, 914.0, 1557.0, 948.0, 1182.0, 948.0], "score": 0.99, "text": "[20] and Baumeister et al. (tilt, 0.91-6.83"}, {"category_id": 15, "poly": [374.0, 1053.0, 1288.0, 1053.0, 1288.0, 1087.0, 374.0, 1087.0], "score": 0.99, "text": ", respectively. However, the tilt and decentration given by AS-OCT instrument are the maximum value of"}, {"category_id": 15, "poly": [1339.0, 1053.0, 1378.0, 1053.0, 1378.0, 1087.0, 1339.0, 1087.0], "score": 1.0, "text": "and"}, {"category_id": 15, "poly": [89.0, 577.0, 434.0, 577.0, 434.0, 612.0, 89.0, 612.0], "score": 0.98, "text": "posterior surfaces. The goodness-of ft"}, {"category_id": 15, "poly": [478.0, 577.0, 713.0, 577.0, 713.0, 612.0, 478.0, 612.0], "score": 0.97, "text": "is between 0.85 and 0.97."}, {"category_id": 15, "poly": [91.0, 1338.0, 1024.0, 1338.0, 1024.0, 1372.0, 91.0, 1372.0], "score": 0.97, "text": "with the decreasing of the number of images. The tilt and decentration changed in the range of 1 degree and"}, {"category_id": 15, "poly": [1112.0, 1338.0, 1562.0, 1338.0, 1562.0, 1372.0, 1112.0, 1372.0], "score": 0.99, "text": "respectively. If the erors were neglected in clinical"}, {"category_id": 15, "poly": [89.0, 1023.0, 157.0, 1021.0, 157.0, 1055.0, 89.0, 1057.0], "score": 1.0, "text": "angle is"}, {"category_id": 15, "poly": [175.0, 1023.0, 1552.0, 1021.0, 1552.0, 1055.0, 175.0, 1057.0], "score": 0.98, "text": ". The two relationships display that both oftit and decentration continuously change in cosine law. The IOL tilt and decentration are the maximum values ofthe"}, {"category_id": 15, "poly": [89.0, 1082.0, 419.0, 1082.0, 419.0, 1116.0, 89.0, 1116.0], "score": 0.99, "text": "scanned images, respectively. Figures"}, {"category_id": 15, "poly": [438.0, 1082.0, 1550.0, 1082.0, 1550.0, 1116.0, 438.0, 1116.0], "score": 0.98, "text": "and 7 show that the errors oftit and decentration produced by AS-OCT are large. In fact, each image contains errors. Ifthese"}, {"category_id": 15, "poly": [89.0, 1308.0, 1028.0, 1308.0, 1028.0, 1342.0, 89.0, 1342.0], "score": 0.97, "text": "90 degrees, and 135 degrees) [19], and 5 (five diferent directions) [22], their results are not verified. Table"}, {"category_id": 15, "poly": [1047.0, 1308.0, 1545.0, 1308.0, 1545.0, 1342.0, 1047.0, 1342.0], "score": 0.96, "text": "shows that the IOL tilt and decentration become smaller "}], "page_info": {"page_no": 3, "height": 2339, "width": 1653}}, {"layout_dets": [{"category_id": 1, "poly": [104.5351791381836, 78.89070892333984, 1570.2327880859375, 78.89070892333984, 1570.2327880859375, 1424.9718017578125, 104.5351791381836, 1424.9718017578125], "score": 0.999968409538269}, {"category_id": 13, "poly": [786, 1189, 801, 1189, 801, 1203, 786, 1203], "score": 0.44, "latex": "\\cdot"}, {"category_id": 13, "poly": [804, 1130, 819, 1130, 819, 1145, 804, 1145], "score": 0.42, "latex": "\\cdot"}, {"category_id": 13, "poly": [743, 85, 757, 85, 757, 101, 743, 101], "score": 0.4, "latex": "\\cdot"}, {"category_id": 13, "poly": [1266, 259, 1280, 259, 1280, 274, 1266, 274], "score": 0.34, "latex": "\\cdot"}, {"category_id": 13, "poly": [1036, 259, 1051, 259, 1051, 274, 1036, 274], "score": 0.31, "latex": "\\cdot"}, {"category_id": 13, "poly": [961, 607, 974, 607, 974, 623, 961, 623], "score": 0.31, "latex": "\\cdot"}, {"category_id": 13, "poly": [743, 1071, 757, 1071, 757, 1087, 743, 1087], "score": 0.3, "latex": "\\cdot"}, {"category_id": 13, "poly": [513, 1071, 527, 1071, 527, 1087, 513, 1087], "score": 0.29, "latex": "\\cdot"}, {"category_id": 13, "poly": [959, 1304, 972, 1304, 972, 1319, 959, 1319], "score": 0.26, "latex": "\\cdot"}, {"category_id": 13, "poly": [514, 85, 527, 85, 527, 100, 514, 100], "score": 0.26, "latex": "\\cdot"}, {"category_id": 13, "poly": [1291, 1362, 1304, 1362, 1304, 1379, 1291, 1379], "score": 0.25, "latex": "\\cdot"}, {"category_id": 13, "poly": [875, 1013, 890, 1013, 890, 1029, 875, 1029], "score": 0.25, "latex": "\\cdot"}, {"category_id": 15, "poly": [116.0, 107.0, 1503.0, 107.0, 1503.0, 141.0, 116.0, 141.0], "score": 0.96, "text": "3. 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{"category_id": 15, "poly": [149.0, 343.0, 264.0, 349.0, 262.0, 383.0, 147.0, 377.0], "score": 0.96, "text": " Presentation"}, {"category_id": 15, "poly": [150.0, 387.0, 305.0, 387.0, 305.0, 422.0, 150.0, 422.0], "score": 0.95, "text": " Full-text available"}, {"category_id": 15, "poly": [140.0, 441.0, 460.0, 438.0, 460.0, 473.0, 140.0, 475.0], "score": 0.99, "text": " Cross Currency Swaption Model"}, {"category_id": 15, "poly": [143.0, 485.0, 239.0, 485.0, 239.0, 519.0, 143.0, 519.0], "score": 0.98, "text": "April 2023"}, {"category_id": 15, "poly": [139.0, 532.0, 271.0, 523.0, 274.0, 560.0, 142.0, 568.0], "score": 0.98, "text": "Tim Xiao"}, {"category_id": 15, "poly": [140.0, 590.0, 1505.0, 592.0, 1505.0, 626.0, 140.0, 624.0], "score": 0.97, "text": "A Cross Curency European Swaption gives the holder the option to enter into a swap to exchange cash flows in two different currencies. 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1045, 1718, 1045, 1747, 991, 1747], "score": 0.26, "latex": "\\mathrm{{Nu}}(\\mathrm{{II}})"}, {"category_id": 15, "poly": [93.0, 136.0, 526.0, 136.0, 526.0, 161.0, 93.0, 161.0], "score": 0.99, "text": "Academic Editors: W. Cantwell and J. M. Deitzel"}, {"category_id": 15, "poly": [89.0, 214.0, 873.0, 214.0, 873.0, 249.0, 89.0, 249.0], "score": 0.98, "text": "distribution, and reproduction in any medium, provided the original work is properly cited."}, {"category_id": 15, "poly": [91.0, 278.0, 180.0, 278.0, 180.0, 305.0, 91.0, 305.0], "score": 1.0, "text": "Abstract"}, {"category_id": 15, "poly": [89.0, 334.0, 1540.0, 334.0, 1540.0, 365.0, 89.0, 365.0], "score": 0.97, "text": "The sorption of Ni(Il) onto grape shell ash (GSA) was studied by performing batch kinetic sorption experiments. The influences of major parameters in Nickel(Il) ions"}, {"category_id": 15, "poly": [91.0, 363.0, 1547.0, 363.0, 1547.0, 395.0, 91.0, 395.0], "score": 0.97, "text": "sorption on GS such as initial of pH, initial concentration of Ni() ions, the initial temperatures of solution, and contact time were investigated. The maximum increase in"}, {"category_id": 15, "poly": [86.0, 424.0, 1547.0, 421.0, 1547.0, 456.0, 86.0, 458.0], "score": 0.97, "text": "rate constants and the equilbrium sorption capacities were calculated. The results indicate that the sorption process follows the second-order kinetics and the values of"}, {"category_id": 15, "poly": [89.0, 487.0, 1545.0, 487.0, 1545.0, 521.0, 89.0, 521.0], "score": 0.97, "text": "adsorption ofNill) on GSA from all the systems were found to be 0.999, and the values ofpredicted equilbrium sorption capacities showed good agreement with the"}, {"category_id": 15, "poly": [86.0, 543.0, 467.0, 546.0, 467.0, 580.0, 86.0, 577.0], "score": 0.97, "text": " that the adsorption process is spontaneous."}, {"category_id": 15, "poly": [91.0, 607.0, 234.0, 607.0, 234.0, 633.0, 91.0, 633.0], "score": 0.97, "text": "1. Introduction"}, {"category_id": 15, "poly": [89.0, 665.0, 1540.0, 665.0, 1540.0, 697.0, 89.0, 697.0], "score": 0.99, "text": "The presence of heavy metals in the environment is of major concern because of their toxic nature and tendency for bioaccumulation in the food chain even in relatively"}, {"category_id": 15, "poly": [89.0, 692.0, 1466.0, 692.0, 1466.0, 724.0, 89.0, 724.0], "score": 0.98, "text": "low concentrations [1-5]. The discharge of water containing heavy metals causes critical polution problems. Nickel (Ml) ion is one such heavy metal frequently"}, {"category_id": 15, "poly": [89.0, 721.0, 1537.0, 721.0, 1537.0, 755.0, 89.0, 755.0], "score": 0.98, "text": "encountered in wastewater streams from industries such as electroplating, battery manufacture, mineral processing, steam-electric power plants, paint formulation, and"}, {"category_id": 15, "poly": [89.0, 850.0, 1547.0, 850.0, 1547.0, 884.0, 89.0, 884.0], "score": 0.96, "text": "and shortness ofbreath, rapid respiration, cyanosis, and extreme weakness [9-12]. These harmful efects ofNi(ll) necessitate its removal from wastewaters before the"}, {"category_id": 15, "poly": [89.0, 877.0, 1562.0, 877.0, 1562.0, 911.0, 89.0, 911.0], "score": 0.98, "text": "release into streams. Several treatment methods such as membrane fitration, chemical precipitation, chemical oxidation/reduction, ion exchange, fitration, electrochemical"}, {"category_id": 15, "poly": [91.0, 909.0, 1557.0, 909.0, 1557.0, 943.0, 91.0, 943.0], "score": 0.99, "text": "treatment, solvent extraction, co-precipitation, and adsorption have been reported for the removal of metallc ions from water and wastewater [13]. Adsorptive removal "}, {"category_id": 15, "poly": [89.0, 938.0, 1528.0, 938.0, 1528.0, 972.0, 89.0, 972.0], "score": 0.99, "text": "is based on the ability ofa porous adsorbent to selectively adsorb some specific compounds from the atmosphere or refinery streans. The compounds, which have a"}, {"category_id": 15, "poly": [89.0, 967.0, 1469.0, 967.0, 1469.0, 1001.0, 89.0, 1001.0], "score": 0.98, "text": "suitable size and shape, can be removed via adsorption. Based on the types of interactions between an adsorbate and a porous sorbent, the adsorption can be"}, {"category_id": 15, "poly": [89.0, 997.0, 1523.0, 997.0, 1523.0, 1031.0, 89.0, 1031.0], "score": 0.98, "text": "categorized as a physical or chemical one [14]. Various porous adsorbents such as activated carbons, zeolites, and mesoporous materials have been investigated for"}, {"category_id": 15, "poly": [89.0, 1026.0, 490.0, 1026.0, 490.0, 1057.0, 89.0, 1057.0], "score": 0.98, "text": "adsorptive removal of hazardous compounds."}, {"category_id": 15, "poly": [86.0, 1070.0, 1530.0, 1072.0, 1530.0, 1113.0, 86.0, 1111.0], "score": 0.79, "text": "A grape is afuitnerryfthe dids wodyvns ofth btancal gesVitisGrapescan atnraor thycaneed formakingjm juic jll, ga"}, {"category_id": 15, "poly": [89.0, 1106.0, 1564.0, 1106.0, 1564.0, 1140.0, 89.0, 1140.0], "score": 0.98, "text": "seed extract, raisins, vinegar, and grape seed oil. Italy ranks first in grape production in the world and Iran ranks eleventh in grape production, a potential of3 millon tons"}, {"category_id": 15, "poly": [86.0, 1131.0, 1542.0, 1131.0, 1542.0, 1172.0, 86.0, 1172.0], "score": 0.92, "text": "of grape are produced anually The total area planted of grape is 310.000 hectare. Thishows a high potentalof grape shell produced during pruning step each year"}, {"category_id": 15, "poly": [89.0, 1165.0, 1542.0, 1165.0, 1542.0, 1196.0, 89.0, 1196.0], "score": 0.98, "text": "that have ittle value. This leads to a need to convert this by-product to usefil, value added product, such as adsorbent. To our knowledge, no investigations have used"}, {"category_id": 15, "poly": [89.0, 1194.0, 583.0, 1194.0, 583.0, 1228.0, 89.0, 1228.0], "score": 0.97, "text": "grape shels as precursor to produce adsorbent and ash."}, {"category_id": 15, "poly": [89.0, 1245.0, 1500.0, 1245.0, 1500.0, 1279.0, 89.0, 1279.0], "score": 0.96, "text": "In this study, we attempt to utilize grape shell waste, an agricutural waste available in Iran as a sorbent to remove Niions from aqueous solution. This study mainly"}, {"category_id": 15, "poly": [91.0, 1274.0, 1540.0, 1274.0, 1540.0, 1308.0, 91.0, 1308.0], "score": 0.95, "text": "focuses on the efect of some environmental parameters such as solution pH, initial Nill) concentration, contact time, and temperature on the abity of Grape Shell ash"}, {"category_id": 15, "poly": [91.0, 1304.0, 1535.0, 1304.0, 1535.0, 1338.0, 91.0, 1338.0], "score": 0.96, "text": "(GSA) to biosorb Nim) ions from aqueous solutions and to determine the mechanism that govern Ni) ions removal as well as to find a suitable kinetic model for the"}, {"category_id": 15, "poly": [87.0, 1330.0, 266.0, 1335.0, 265.0, 1370.0, 86.0, 1364.0], "score": 0.99, "text": "adsorption process."}, {"category_id": 15, "poly": [91.0, 1396.0, 246.0, 1396.0, 246.0, 1423.0, 91.0, 1423.0], "score": 0.97, "text": "2. Expe rime ntal"}, {"category_id": 15, "poly": [86.0, 1450.0, 352.0, 1447.0, 352.0, 1481.0, 86.0, 1484.0], "score": 0.95, "text": "2.1. Preparation of the Ads orbent"}, {"category_id": 15, "poly": [91.0, 1508.0, 1560.0, 1508.0, 1560.0, 1540.0, 91.0, 1540.0], "score": 0.98, "text": "GS was obtained from one ofthe villages of Arak in Iran. Unmodified sorbent was washed several times with warm distilled water to remove impurities and was dried at"}, {"category_id": 15, "poly": [89.0, 1601.0, 335.0, 1601.0, 335.0, 1632.0, 89.0, 1632.0], "score": 0.96, "text": "stored in air glass container."}, {"category_id": 15, "poly": [91.0, 1662.0, 199.0, 1662.0, 199.0, 1688.0, 91.0, 1688.0], "score": 0.97, "text": "2.2.Reagents"}, {"category_id": 15, "poly": [89.0, 1818.0, 229.0, 1818.0, 229.0, 1844.0, 89.0, 1844.0], "score": 0.99, "text": "analytical grade."}, {"category_id": 15, "poly": [89.0, 1874.0, 207.0, 1874.0, 207.0, 1908.0, 89.0, 1908.0], "score": 0.98, "text": "2.3. Apparatus"}, {"category_id": 15, "poly": [86.0, 1927.0, 1510.0, 1930.0, 1510.0, 1964.0, 86.0, 1961.0], "score": 0.98, "text": " The Ni ion concentration in the solutions was determined by Atomic Absorption Spectrometer (model AA 680 made of SHIMADZU) using a standard calibration"}, {"category_id": 15, "poly": [89.0, 2020.0, 369.0, 2020.0, 369.0, 2051.0, 89.0, 2051.0], "score": 0.99, "text": "2.4. Batch Ads orption Experiments"}, {"category_id": 15, "poly": [89.0, 2073.0, 1508.0, 2073.0, 1508.0, 2108.0, 89.0, 2108.0], "score": 0.98, "text": "Batch experiments were conducted in order to study the efect ofimportant parameters like the pH, contact time, and the initial ion concentration on the adsorptive"}, {"category_id": 15, "poly": [91.0, 2168.0, 1555.0, 2168.0, 1555.0, 2203.0, 91.0, 2203.0], "score": 0.99, "text": "onto the GSA was studied across a pH range of2.0-5.0 in different time with a fixed adsorbent concentration. The effect ofthe initial concentration and contact time on"}, {"category_id": 15, "poly": [91.0, 2203.0, 1498.0, 2203.0, 1498.0, 2237.0, 91.0, 2237.0], "score": 0.96, "text": "the uptake of the Ni ions was conducted by varying the ion concentration from 5.0 to 50.0 mg L-1 at different contact times (0.0-90.0 min). The percent of Ni(II)"}, {"category_id": 15, "poly": [91.0, 819.0, 481.0, 819.0, 481.0, 853.0, 91.0, 853.0], "score": 0.98, "text": "lethal in humans at atmospheric exposures of"}, {"category_id": 15, "poly": [243.0, 1749.0, 1545.0, 1749.0, 1545.0, 1783.0, 243.0, 1783.0], "score": 0.97, "text": "in double distiled water. Working solutions of the desired concentration were then prepared by successive dilution. All the solutions were made using"}, {"category_id": 15, "poly": [89.0, 1783.0, 639.0, 1783.0, 639.0, 1815.0, 89.0, 1815.0], "score": 0.99, "text": "deionized distilled water. pH adjustments were performed with"}, {"category_id": 15, "poly": [704.0, 1783.0, 1478.0, 1783.0, 1478.0, 1815.0, 704.0, 1815.0], "score": 0.98, "text": "and NaOH (Merck) solutions 0.1 N. A chemicals used in the experiments were reagent"}, {"category_id": 15, "poly": [86.0, 750.0, 998.0, 750.0, 998.0, 792.0, 86.0, 792.0], "score": 0.91, "text": "porcelain enamelng [68] In drinking water and forindustrial wastewater, the tolerance lmit ofnickel is"}, {"category_id": 15, "poly": [195.0, 1562.0, 426.0, 1567.0, 426.0, 1608.0, 195.0, 1603.0], "score": 0.97, "text": "from room temperature to"}, {"category_id": 15, "poly": [89.0, 782.0, 1247.0, 782.0, 1247.0, 816.0, 89.0, 816.0], "score": 0.98, "text": "created. Dermatitis (nickel itch) is the most frequent effect ofexposure to nickel, such as coins and costume jewelry. Nickel carbonyl"}, {"category_id": 15, "poly": [1345.0, 782.0, 1542.0, 782.0, 1542.0, 816.0, 1345.0, 816.0], "score": 0.98, "text": "has been estimated as"}, {"category_id": 15, "poly": [1521.0, 397.0, 1562.0, 397.0, 1562.0, 429.0, 1521.0, 429.0], "score": 1.0, "text": "The"}, {"category_id": 15, "poly": [1111.0, 750.0, 1148.0, 750.0, 1148.0, 792.0, 1111.0, 792.0], "score": 1.0, "text": "and"}, {"category_id": 15, "poly": [1249.0, 750.0, 1567.0, 750.0, 1567.0, 792.0, 1249.0, 792.0], "score": 0.91, "text": ".Cancer ofnose, bone, and ungs is"}, {"category_id": 15, "poly": [84.0, 1713.0, 839.0, 1715.0, 839.0, 1757.0, 84.0, 1754.0], "score": 0.79, "text": "Solutionfmtalns (nkeltratewas ofaaltical gadeytetic stock t"}, {"category_id": 15, "poly": [86.0, 2105.0, 689.0, 2103.0, 689.0, 2144.0, 86.0, 2147.0], "score": 0.97, "text": "removal ofNion using GSA. For the batch adsorption experiments,"}, {"category_id": 15, "poly": [753.0, 2105.0, 1101.0, 2103.0, 1101.0, 2144.0, 753.0, 2147.0], "score": 0.86, "text": "sohutionofNi ofinitialconcentration"}, {"category_id": 15, "poly": [89.0, 185.0, 180.0, 185.0, 180.0, 217.0, 89.0, 217.0], "score": 1.0, "text": "Copyright"}, {"category_id": 15, "poly": [205.0, 185.0, 1513.0, 185.0, 1513.0, 217.0, 205.0, 217.0], "score": 0.98, "text": "2013 Nahid Ghasemi et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use,"}, {"category_id": 15, "poly": [89.0, 397.0, 666.0, 397.0, 666.0, 429.0, 89.0, 429.0], "score": 0.95, "text": "the rate of sorption of Ni(l) ions on GS was observed at an initial"}, {"category_id": 15, "poly": [1195.0, 2105.0, 1370.0, 2103.0, 1370.0, 2144.0, 1195.0, 2147.0], "score": 0.94, "text": "was contacted with"}, {"category_id": 15, "poly": [1483.0, 2105.0, 1528.0, 2103.0, 1528.0, 2144.0, 1483.0, 2147.0], "score": 1.0, "text": "The"}, {"category_id": 15, "poly": [89.0, 2139.0, 563.0, 2139.0, 563.0, 2173.0, 89.0, 2173.0], "score": 0.99, "text": "contents were placed in a stirrer and gently agitated at"}, {"category_id": 15, "poly": [647.0, 2139.0, 1523.0, 2139.0, 1523.0, 2173.0, 647.0, 2173.0], "score": 0.97, "text": "The solution was fitered, and the residual Ni concentration was analyzed. The effect of the initial pH"}, {"category_id": 15, "poly": [736.0, 397.0, 1298.0, 397.0, 1298.0, 429.0, 736.0, 429.0], "score": 0.96, "text": " initial concentration of nickel 50 mgL, temperature of solution"}, {"category_id": 15, "poly": [1373.0, 397.0, 1417.0, 397.0, 1417.0, 429.0, 1373.0, 429.0], "score": 0.96, "text": ", and"}, {"category_id": 15, "poly": [742.0, 1533.0, 1567.0, 1535.0, 1567.0, 1569.0, 742.0, 1567.0], "score": 0.98, "text": " The material was placed in a vertical stainless steel reactor and heated in a furnace at a rate of"}, {"category_id": 15, "poly": [492.0, 1562.0, 1326.0, 1567.0, 1326.0, 1608.0, 492.0, 1603.0], "score": 0.97, "text": " The black residue was cooled and sieved to get GS ash (GSA) with an average paricle size of"}, {"category_id": 15, "poly": [1422.0, 1562.0, 1515.0, 1567.0, 1515.0, 1608.0, 1422.0, 1603.0], "score": 0.92, "text": "and finally"}, {"category_id": 15, "poly": [576.0, 819.0, 606.0, 819.0, 606.0, 853.0, 576.0, 853.0], "score": 1.0, "text": "for"}, {"category_id": 15, "poly": [672.0, 819.0, 1535.0, 819.0, 1535.0, 853.0, 672.0, 853.0], "score": 0.98, "text": "[3]. Acute Ni(ll) poisoning causes dizziness, headache, nausea and vomiting, chest pain, dry cough"}, {"category_id": 15, "poly": [153.0, 1533.0, 184.0, 1535.0, 184.0, 1569.0, 153.0, 1567.0], "score": 1.0, "text": "for"}, {"category_id": 15, "poly": [229.0, 1533.0, 666.0, 1535.0, 666.0, 1569.0, 229.0, 1567.0], "score": 0.98, "text": "and cut into small pieces of sizes between 2.0 and"}, {"category_id": 15, "poly": [91.0, 458.0, 903.0, 458.0, 903.0, 490.0, 91.0, 490.0], "score": 0.98, "text": "rate constants were found to be 0.224, 0.402, 0.193 and 0.123 min at 298, 308, 318, and"}, {"category_id": 15, "poly": [965.0, 458.0, 1471.0, 458.0, 1471.0, 490.0, 965.0, 490.0], "score": 0.98, "text": " respectively. The values of correlation coefficients for the"}, {"category_id": 15, "poly": [89.0, 1961.0, 613.0, 1961.0, 613.0, 1993.0, 89.0, 1993.0], "score": 0.98, "text": "curve. The pH was measured via the Swiss-made Metrohm"}, {"category_id": 15, "poly": [688.0, 1961.0, 1031.0, 1961.0, 1031.0, 1993.0, 688.0, 1993.0], "score": 0.99, "text": "meter with a combined glass electrode."}, {"category_id": 15, "poly": [89.0, 517.0, 718.0, 517.0, 718.0, 551.0, 89.0, 551.0], "score": 0.98, "text": "experimental equilibrium uptake values. The thermodynamic parameters"}, {"category_id": 15, "poly": [822.0, 517.0, 1557.0, 517.0, 1557.0, 551.0, 822.0, 551.0], "score": 0.97, "text": ", and S\") of the adsorption process were calculated, and these parameters showed"}, {"category_id": 15, "poly": [961.0, 1713.0, 990.0, 1715.0, 990.0, 1757.0, 961.0, 1754.0], "score": 0.82, "text": "off"}, {"category_id": 15, "poly": [1046.0, 1713.0, 1545.0, 1715.0, 1545.0, 1757.0, 1046.0, 1754.0], "score": 0.92, "text": "ions was prepared by dissolving the requred quanty of"}], "page_info": {"page_no": 1, "height": 2339, "width": 1653}}, {"layout_dets": [{"category_id": 1, "poly": [91.9344482421875, 690.4903564453125, 1550.9111328125, 690.4903564453125, 1550.9111328125, 779.0286865234375, 91.9344482421875, 779.0286865234375], "score": 0.9999997019767761}, {"category_id": 1, "poly": [91.05098724365234, 360.5782470703125, 453.71307373046875, 360.5782470703125, 453.71307373046875, 387.5991516113281, 91.05098724365234, 387.5991516113281], "score": 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336.0, 86.0, 336.0], "score": 0.97, "text": " 3. Results and Discussion"}, {"category_id": 15, "poly": [89.0, 361.0, 448.0, 363.0, 448.0, 395.0, 88.0, 392.0], "score": 0.98, "text": "3.1. Effects of Solution pH and Agitation Time"}, {"category_id": 15, "poly": [89.0, 419.0, 1552.0, 419.0, 1552.0, 451.0, 89.0, 451.0], "score": 0.97, "text": "One ofthe main parameters affecting the metal adsorption from aqueous solution is the pH ofthe solution. The influence of solution pH and agitation time on the removal"}, {"category_id": 15, "poly": [89.0, 451.0, 1557.0, 451.0, 1557.0, 482.0, 89.0, 482.0], "score": 0.98, "text": "of Ni() by GSA was represented in Figure 1 and Table 1, for a period of 90 min. With increasing pH from 2 to 5, adsorption capacity ofadsorbent increased from 7.2"}, {"category_id": 15, "poly": [89.0, 724.0, 1535.0, 724.0, 1535.0, 755.0, 89.0, 755.0], "score": 0.98, "text": "contrary, as the pH increases, the adsorbent surface becomes more and more negatively charged, and the adsorption ofNil) ions is more favorable. Figure 1 shows "}, {"category_id": 15, "poly": [89.0, 753.0, 1070.0, 753.0, 1070.0, 785.0, 89.0, 785.0], "score": 0.98, "text": "that the Ni(Il) removal by GSA increases with increase in pH and the maximum of removal attains at 20 minutes."}, {"category_id": 15, "poly": [89.0, 811.0, 512.0, 814.0, 512.0, 841.0, 88.0, 838.0], "score": 0.99, "text": "3.2. Effect of Initial Concentration and Agitation Time"}, {"category_id": 15, "poly": [91.0, 936.0, 1567.0, 936.0, 1567.0, 967.0, 91.0, 967.0], "score": 0.98, "text": "adsorption sites in adsorbent that is high at higher initial concentrations. Thus, at the same time, the time required for attaining the equilibrium state is highly independent on"}, {"category_id": 15, "poly": [86.0, 960.0, 1491.0, 962.0, 1491.0, 997.0, 86.0, 994.0], "score": 0.96, "text": " initial NiMl) concentration. In Figure 2, the infuence of contact time on the adsorption of NiIl) on GSA is observed. According to Figure 2, the amount ofNi(I)"}, {"category_id": 15, "poly": [91.0, 994.0, 1550.0, 994.0, 1550.0, 1028.0, 91.0, 1028.0], "score": 0.98, "text": "adsorption onto GSA increases sharply up to the first 10 minutes and finally attain equilbrium where there is no further increase in the amount of adsorption The uptake"}, {"category_id": 15, "poly": [89.0, 1174.0, 1080.0, 1174.0, 1080.0, 1206.0, 89.0, 1206.0], "score": 0.98, "text": "Table 3: Comparison of adsorption capacity of various adsorbents for the removal of Ni(ll) from aqueous phase."}, {"category_id": 15, "poly": [86.0, 1301.0, 327.0, 1301.0, 327.0, 1333.0, 86.0, 1333.0], "score": 0.97, "text": "3.3. Adsorption Kinetic Study"}, {"category_id": 15, "poly": [89.0, 1357.0, 1525.0, 1357.0, 1525.0, 1389.0, 89.0, 1389.0], "score": 0.99, "text": "Determination of uptake kinetics is important for the evaluation ofa candidate adsorbent material. In order to estimate the uptake capacity ofthe sample in this study,"}, {"category_id": 15, "poly": [89.0, 1384.0, 1520.0, 1384.0, 1520.0, 1418.0, 89.0, 1418.0], "score": 0.98, "text": "three sorption kinetic models developed, pseudo-first-order, pseudo-second-order and Elovich equations by Lagergren [19], Ho and McKay [20], and Fatehi et al."}, {"category_id": 15, "poly": [89.0, 1413.0, 352.0, 1413.0, 352.0, 1445.0, 89.0, 1445.0], "score": 0.99, "text": "[21], respectively, were used."}, {"category_id": 15, "poly": [867.0, 1663.0, 945.0, 1670.0, 943.0, 1696.0, 865.0, 1690.0], "score": 0.91, "text": "t),(5)."}, {"category_id": 15, "poly": [89.0, 1915.0, 1555.0, 1915.0, 1555.0, 1949.0, 89.0, 1949.0], "score": 0.98, "text": "due to a boundary layer or external resistance controllng at the begining of the sorption process [22]. In most cases ofthe literature, the pseudo- first-order model does"}, {"category_id": 15, "poly": [91.0, 1974.0, 1510.0, 1974.0, 1510.0, 2008.0, 91.0, 2008.0], "score": 0.96, "text": "sorption capacity ofthe solid phase. Contrary to other well established models, it predicts the behavior over the whole range of studies and it is in agreement with a"}, {"category_id": 15, "poly": [89.0, 2003.0, 625.0, 2003.0, 625.0, 2037.0, 89.0, 2037.0], "score": 0.97, "text": "chemisorption mechanism being the rate-controling step [22]"}, {"category_id": 15, "poly": [89.0, 2088.0, 1532.0, 2088.0, 1532.0, 2122.0, 89.0, 2122.0], "score": 0.98, "text": "Table 4: The pseudo-first-order, pseudo-second-order, and Elovich's equation kinetic parameters for Nill) sorption onto GSA at different temperatures of solution."}, {"category_id": 15, "poly": [206.0, 1713.0, 605.0, 1718.0, 605.0, 1752.0, 206.0, 1747.0], "score": 0.97, "text": "is related to the available sites for adsorption."}, {"category_id": 15, "poly": [1368.0, 1681.0, 1542.0, 1681.0, 1542.0, 1715.0, 1368.0, 1715.0], "score": 0.98, "text": ", and the parameter"}, {"category_id": 15, "poly": [86.0, 1764.0, 1283.0, 1766.0, 1283.0, 1801.0, 86.0, 1798.0], "score": 0.97, "text": " Initially, the validity of the two models was checked by studying the kinetics under different intial temperatures of solution. Linear plots of"}, {"category_id": 15, "poly": [1402.0, 1764.0, 1441.0, 1766.0, 1441.0, 1801.0, 1402.0, 1798.0], "score": 1.0, "text": "and"}, {"category_id": 15, "poly": [1483.0, 1764.0, 1560.0, 1766.0, 1559.0, 1801.0, 1483.0, 1798.0], "score": 0.98, "text": "versus t"}, {"category_id": 15, "poly": [89.0, 906.0, 169.0, 906.0, 169.0, 938.0, 89.0, 938.0], "score": 1.0, "text": "4.344 to"}, {"category_id": 15, "poly": [302.0, 906.0, 1520.0, 906.0, 1520.0, 938.0, 302.0, 938.0], "score": 0.95, "text": "with the increasing in initial Ni(ll) concentration. This increase may be due to the ratio of the initial number of moles of Ni(ll) to the available"}, {"category_id": 15, "poly": [87.0, 480.0, 110.0, 485.0, 110.0, 519.0, 86.0, 514.0], "score": 1.0, "text": "to"}, {"category_id": 15, "poly": [1223.0, 183.0, 1278.0, 183.0, 1278.0, 214.0, 1223.0, 214.0], "score": 1.0, "text": "where"}, {"category_id": 15, "poly": [714.0, 1606.0, 1018.0, 1606.0, 1018.0, 1637.0, 714.0, 1637.0], "score": 1.0, "text": "is the rate constants of adsorption."}, {"category_id": 15, "poly": [1308.0, 183.0, 1346.0, 183.0, 1346.0, 214.0, 1308.0, 214.0], "score": 1.0, "text": "and"}, {"category_id": 15, "poly": [1373.0, 183.0, 1542.0, 183.0, 1542.0, 214.0, 1373.0, 214.0], "score": 1.0, "text": "are the equilibrium"}, {"category_id": 15, "poly": [89.0, 1886.0, 1171.0, 1886.0, 1171.0, 1920.0, 89.0, 1920.0], "score": 0.96, "text": "pseudo-frst-order model to ft the kinetic data for the initial concentrations examined. The reason for these diferences in the"}, {"category_id": 15, "poly": [1196.0, 1886.0, 1552.0, 1886.0, 1552.0, 1920.0, 1196.0, 1920.0], "score": 0.99, "text": "values is that there is a time lag, possibly"}, {"category_id": 15, "poly": [1058.0, 1798.0, 1096.0, 1798.0, 1096.0, 1830.0, 1058.0, 1830.0], "score": 1.0, "text": "and"}, {"category_id": 15, "poly": [1123.0, 1798.0, 1520.0, 1798.0, 1520.0, 1830.0, 1123.0, 1830.0], "score": 0.96, "text": "values were calculated from the slopes ofthe"}, {"category_id": 15, "poly": [649.0, 1606.0, 687.0, 1606.0, 687.0, 1637.0, 649.0, 1637.0], "score": 1.0, "text": "and"}, {"category_id": 15, "poly": [89.0, 636.0, 1075.0, 633.0, 1075.0, 668.0, 89.0, 670.0], "score": 0.96, "text": "Figure 1: The influence of solution pH and agitation time on the removal ofNi(ll) by GSA (Ni(ll) concentration,"}, {"category_id": 15, "poly": [89.0, 1944.0, 914.0, 1944.0, 914.0, 1978.0, 89.0, 1978.0], "score": 0.97, "text": "not ft the kinetic data well for the whole range ofcontact time, and generally underestimate the"}, {"category_id": 15, "poly": [939.0, 1944.0, 1510.0, 1944.0, 1510.0, 1978.0, 939.0, 1978.0], "score": 0.99, "text": "values [23, 24]. The pseudo-second order model is based on the"}, {"category_id": 15, "poly": [1306.0, 1569.0, 1530.0, 1567.0, 1530.0, 1601.0, 1306.0, 1603.0], "score": 0.97, "text": "are the amounts ofNi(lI)"}, {"category_id": 15, "poly": [1154.0, 1569.0, 1219.0, 1567.0, 1219.0, 1601.0, 1154.0, 1603.0], "score": 1.0, "text": "where"}, {"category_id": 15, "poly": [1244.0, 1569.0, 1283.0, 1567.0, 1283.0, 1601.0, 1244.0, 1603.0], "score": 1.0, "text": "and"}, {"category_id": 15, "poly": [89.0, 1857.0, 942.0, 1857.0, 942.0, 1891.0, 89.0, 1891.0], "score": 0.98, "text": "coeficients of the pseudo-frst-order kinetic were found to be lower than 0.76, and the calculated"}, {"category_id": 15, "poly": [967.0, 1857.0, 1212.0, 1857.0, 1212.0, 1891.0, 967.0, 1891.0], "score": 0.98, "text": "is not equal to experimental"}, {"category_id": 15, "poly": [1235.0, 1857.0, 1510.0, 1857.0, 1510.0, 1891.0, 1235.0, 1891.0], "score": 0.97, "text": ", suggesting the insufficiency of"}, {"category_id": 15, "poly": [677.0, 183.0, 927.0, 183.0, 927.0, 214.0, 677.0, 214.0], "score": 0.96, "text": ", were calculated as follows:"}, {"category_id": 15, "poly": [1168.0, 636.0, 1280.0, 633.0, 1280.0, 668.0, 1168.0, 670.0], "score": 0.94, "text": ", GSA dose,"}, {"category_id": 15, "poly": [91.0, 872.0, 984.0, 872.0, 984.0, 906.0, 91.0, 906.0], "score": 0.97, "text": "Figure 2 and Table 2 represent the removal of NiM) as a function of initial concentrations ranging from"}, {"category_id": 15, "poly": [1102.0, 872.0, 1532.0, 872.0, 1532.0, 906.0, 1102.0, 906.0], "score": 0.97, "text": "by GSA. The uptake eficiency is increased from"}, {"category_id": 15, "poly": [86.0, 2225.0, 978.0, 2222.0, 978.0, 2256.0, 86.0, 2259.0], "score": 0.96, "text": "Figure 4: The pseudo second order plots for the adsorption of Ni(ll) by GSA. (Ni(ll) concentration,"}, {"category_id": 15, "poly": [89.0, 692.0, 425.0, 692.0, 425.0, 724.0, 89.0, 724.0], "score": 0.98, "text": "In lower pH, a higher concentration of"}, {"category_id": 15, "poly": [458.0, 692.0, 1542.0, 692.0, 1542.0, 724.0, 458.0, 724.0], "score": 0.97, "text": "ions present in the mixture competes with Ni(ll) ions for the adsorption sites resulting in the reduced uptake ofNi(Il). On the"}, {"category_id": 15, "poly": [614.0, 217.0, 1035.0, 217.0, 1035.0, 249.0, 614.0, 249.0], "score": 0.94, "text": "is equilibrium Ni(ll) concentration on adsorbent"}, {"category_id": 15, "poly": [920.0, 1681.0, 983.0, 1681.0, 983.0, 1715.0, 920.0, 1715.0], "score": 1.0, "text": "where"}, {"category_id": 15, "poly": [999.0, 1681.0, 1239.0, 1681.0, 1239.0, 1715.0, 999.0, 1715.0], "score": 0.98, "text": "is the initial adsorption rate"}, {"category_id": 15, "poly": [89.0, 217.0, 387.0, 217.0, 387.0, 249.0, 89.0, 249.0], "score": 0.95, "text": "and initial concentrations of Ni(I)"}, {"category_id": 15, "poly": [464.0, 217.0, 589.0, 217.0, 589.0, 249.0, 464.0, 249.0], "score": 0.97, "text": ", respectively;"}, {"category_id": 15, "poly": [1108.0, 217.0, 1491.0, 217.0, 1491.0, 249.0, 1108.0, 249.0], "score": 0.96, "text": "); V is the volume ofNi() solution (L); and"}, {"category_id": 15, "poly": [1515.0, 217.0, 1537.0, 217.0, 1537.0, 249.0, 1515.0, 249.0], "score": 1.0, "text": "is"}, {"category_id": 15, "poly": [89.0, 1798.0, 905.0, 1798.0, 905.0, 1830.0, 89.0, 1830.0], "score": 0.97, "text": "showed the applicability ofthe above equations (the first and second order) for GSA (Figures"}, {"category_id": 15, "poly": [89.0, 1243.0, 953.0, 1238.0, 953.0, 1269.0, 89.0, 1274.0], "score": 0.98, "text": "Figure 2: The influence of initial concentration and agitation time on the removal ofNi(l) by GSA"}, {"category_id": 15, "poly": [89.0, 183.0, 165.0, 183.0, 165.0, 214.0, 89.0, 214.0], "score": 1.0, "text": "removal"}, {"category_id": 15, "poly": [216.0, 183.0, 653.0, 183.0, 653.0, 214.0, 216.0, 214.0], "score": 0.96, "text": " and the amount of adsorbed Ni(lI) at equilibrium,"}, {"category_id": 15, "poly": [1347.0, 636.0, 1485.0, 633.0, 1485.0, 668.0, 1347.0, 670.0], "score": 0.92, "text": "; Agitation time,"}, {"category_id": 15, "poly": [1310.0, 1243.0, 1449.0, 1238.0, 1449.0, 1269.0, 1310.0, 1274.0], "score": 1.0, "text": "; Agitation time,"}, {"category_id": 15, "poly": [1131.0, 1243.0, 1243.0, 1238.0, 1243.0, 1269.0, 1131.0, 1274.0], "score": 1.0, "text": "; GSA dose,"}, {"category_id": 15, "poly": [1067.0, 2225.0, 1179.0, 2222.0, 1179.0, 2256.0, 1067.0, 2259.0], "score": 0.97, "text": ", GSA dose,"}, {"category_id": 15, "poly": [997.0, 1827.0, 1159.0, 1827.0, 1159.0, 1861.0, 997.0, 1861.0], "score": 0.98, "text": "versus Int (Figure"}, {"category_id": 15, "poly": [1180.0, 1827.0, 1513.0, 1827.0, 1513.0, 1861.0, 1180.0, 1861.0], "score": 0.99, "text": " are presented in Table 4. Correlation"}, {"category_id": 15, "poly": [86.0, 244.0, 357.0, 246.0, 357.0, 280.0, 86.0, 278.0], "score": 0.98, "text": "the mass ofGSA sample used"}, {"category_id": 15, "poly": [925.0, 1798.0, 961.0, 1798.0, 961.0, 1830.0, 925.0, 1830.0], "score": 1.0, "text": "and"}, {"category_id": 15, "poly": [979.0, 1798.0, 1031.0, 1798.0, 1031.0, 1830.0, 979.0, 1830.0], "score": 0.96, "text": "). The"}, {"category_id": 15, "poly": [89.0, 570.0, 714.0, 570.0, 714.0, 602.0, 89.0, 602.0], "score": 0.97, "text": "Table 1: The maximum amount of Ni(Il) sorbate as a function of pH at"}, {"category_id": 15, "poly": [86.0, 1021.0, 927.0, 1023.0, 927.0, 1057.0, 86.0, 1055.0], "score": 0.98, "text": " of adsorption of other adsorbents for the removal of Ni(Il) from aqueous phase is given in Table"}, {"category_id": 15, "poly": [948.0, 1021.0, 1164.0, 1023.0, 1163.0, 1057.0, 948.0, 1055.0], "score": 0.96, "text": "for comparison [15-18]"}, {"category_id": 15, "poly": [91.0, 1684.0, 551.0, 1684.0, 551.0, 1715.0, 91.0, 1715.0], "score": 0.97, "text": "The simplified form of Elovich's equation is shown in"}, {"category_id": 15, "poly": [582.0, 1684.0, 603.0, 1684.0, 603.0, 1715.0, 582.0, 1715.0], "score": 0.94, "text": "is"}, {"category_id": 15, "poly": [86.0, 1106.0, 394.0, 1109.0, 394.0, 1143.0, 86.0, 1140.0], "score": 0.98, "text": "Table 2: The maximum amount of"}, {"category_id": 15, "poly": [450.0, 1106.0, 1038.0, 1109.0, 1038.0, 1143.0, 450.0, 1140.0], "score": 0.96, "text": "sorbate as a function of initial concentration of Ni(ll) at 40 minutes."}, {"category_id": 15, "poly": [89.0, 1827.0, 706.0, 1827.0, 706.0, 1861.0, 89.0, 1861.0], "score": 0.97, "text": "linear plots and are presented in Table 4. The Elovich constants (a and"}, {"category_id": 15, "poly": [723.0, 1827.0, 974.0, 1827.0, 974.0, 1861.0, 723.0, 1861.0], "score": 0.98, "text": ") computed from the plots of"}, {"category_id": 15, "poly": [84.0, 1564.0, 549.0, 1567.0, 549.0, 1608.0, 84.0, 1606.0], "score": 0.95, "text": "The frst and scond orderate expressions given by"}, {"category_id": 15, "poly": [580.0, 1564.0, 807.0, 1567.0, 807.0, 1608.0, 580.0, 1606.0], "score": 0.97, "text": "and (4) are respectively,"}, {"category_id": 15, "poly": [89.0, 1606.0, 537.0, 1606.0, 537.0, 1637.0, 89.0, 1637.0], "score": 0.97, "text": "adsorbed (mg g ) at equilibrium time and at time t"}, {"category_id": 15, "poly": [583.0, 1606.0, 622.0, 1606.0, 622.0, 1637.0, 583.0, 1637.0], "score": 1.0, "text": "and"}], "page_info": {"page_no": 2, "height": 2339, "width": 1653}}, {"layout_dets": [{"category_id": 1, "poly": [88.7582015991211, 1832.003662109375, 1155.3814697265625, 1832.003662109375, 1155.3814697265625, 1862.21630859375, 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205.0, 91.0, 205.0], "score": 0.97, "text": "The values of correlation coefficients for the adsorption of Nill) on GSA from allthe systems were found to be 0.999 for pseudo-second-order kinetic model, and the"}, {"category_id": 15, "poly": [91.0, 431.0, 199.0, 431.0, 199.0, 458.0, 91.0, 458.0], "score": 1.0, "text": "temperature."}, {"category_id": 15, "poly": [86.0, 485.0, 310.0, 485.0, 310.0, 517.0, 86.0, 517.0], "score": 0.98, "text": "3.4. Ads orption Mechanism"}, {"category_id": 15, "poly": [91.0, 543.0, 1508.0, 543.0, 1508.0, 577.0, 91.0, 577.0], "score": 0.97, "text": "To confirm whether Ni ions adsorption on GSA is dominated by intraparticle difusion (Weber and Morris), the empirical data were analyzed using the intraparticle"}, {"category_id": 15, "poly": [91.0, 670.0, 1545.0, 670.0, 1545.0, 704.0, 91.0, 704.0], "score": 0.97, "text": "passed through the origin, showing that intraparticle difusion was not sole rate-controling step although it was involved in the process. This emphasized that adsorption"}, {"category_id": 15, "poly": [89.0, 702.0, 551.0, 702.0, 551.0, 733.0, 89.0, 733.0], "score": 0.97, "text": "of Ni(l) ions was a two or more steps process [26]."}, {"category_id": 15, "poly": [91.0, 787.0, 1139.0, 787.0, 1139.0, 819.0, 91.0, 819.0], "score": 0.97, "text": "Table 5: The intraparticle difusion kinetic parameters for Nill) sorption onto GSA at different temperatures of solution."}, {"category_id": 15, "poly": [89.0, 914.0, 394.0, 914.0, 394.0, 945.0, 89.0, 945.0], "score": 0.99, "text": "3.5. Adsorption Thermodynamic Study"}, {"category_id": 15, "poly": [1350.0, 1009.0, 1387.0, 1009.0, 1387.0, 1040.0, 1350.0, 1040.0], "score": 0.99, "text": "(7)"}, {"category_id": 15, "poly": [89.0, 1296.0, 1545.0, 1296.0, 1545.0, 1330.0, 89.0, 1330.0], "score": 0.98, "text": "endothermic nature ofthe sorption process. Since difusion is an exothermic process, it would be expected that increased solution temperature would result in decrease"}, {"category_id": 15, "poly": [91.0, 1330.0, 1355.0, 1330.0, 1355.0, 1364.0, 91.0, 1364.0], "score": 0.94, "text": "uptake of NiMl) ions from aqueous solution. Also, the negative value of \u25b3S\u00b0 (-0.0276 kJ mol I K-1) may be related to the decrease randommess."}, {"category_id": 15, "poly": [86.0, 1411.0, 733.0, 1413.0, 733.0, 1455.0, 86.0, 1452.0], "score": 0.95, "text": "Table 6: Thermodynanmic parameters for adsorption of Nil) onto GSA."}, {"category_id": 15, "poly": [91.0, 1542.0, 224.0, 1542.0, 224.0, 1569.0, 91.0, 1569.0], "score": 1.0, "text": "4. Conclusion"}, {"category_id": 15, "poly": [89.0, 1598.0, 1550.0, 1598.0, 1550.0, 1632.0, 89.0, 1632.0], "score": 0.98, "text": "The sorption characteristics of Grape Shell were studied for Ni(ll). The results indicated that this adsorbent may be used as an inexpensive and effective material for the"}, {"category_id": 15, "poly": [91.0, 1628.0, 1523.0, 1628.0, 1523.0, 1662.0, 91.0, 1662.0], "score": 0.97, "text": "removal ofNi) from aqueous solutions but with a low efficiency. The sorption process was affected by experimental conditions such as pH, initial concentration of"}, {"category_id": 15, "poly": [89.0, 1657.0, 1528.0, 1657.0, 1528.0, 1691.0, 89.0, 1691.0], "score": 0.97, "text": "Ni) ions, the initial temperatures of solution, and contact time. Analysis ofthe kinetic data showed that the kinetics ofNi adsorption using Grape Shllash as an"}, {"category_id": 15, "poly": [89.0, 1684.0, 1535.0, 1686.0, 1535.0, 1720.0, 89.0, 1718.0], "score": 0.98, "text": "adsorbent for different values of initial temperatures of soution is explained by the second-order-kinetic model. The calculated thermodynamic parameters determined"}, {"category_id": 15, "poly": [89.0, 1715.0, 831.0, 1715.0, 831.0, 1747.0, 89.0, 1747.0], "score": 0.97, "text": "the spontaneous and endothermic nature of the Ni(ll) biosorption process onto GSA."}, {"category_id": 15, "poly": [93.0, 1779.0, 261.0, 1779.0, 261.0, 1805.0, 93.0, 1805.0], "score": 1.0, "text": "Acknowedgment"}, {"category_id": 15, "poly": [89.0, 1832.0, 1151.0, 1832.0, 1151.0, 1864.0, 89.0, 1864.0], "score": 0.99, "text": "The authors would like to thank the Islamic Azad University, Arak Branch, for providing the research fund for this project"}, {"category_id": 15, "poly": [87.0, 1890.0, 207.0, 1896.0, 205.0, 1930.0, 86.0, 1924.0], "score": 0.97, "text": "References"}, {"category_id": 15, "poly": [113.0, 1949.0, 1552.0, 1952.0, 1552.0, 1986.0, 113.0, 1983.0], "score": 0.97, "text": "1. A. Bhatnagar and A. K. Minocha, \u201cBiosorption optimization of nickel removal from water using Punica granatum peel waste,\u2032 Colloids and Surfaces B, vol. 76,"}, {"category_id": 15, "poly": [108.0, 2005.0, 1562.0, 2008.0, 1562.0, 2049.0, 108.0, 2047.0], "score": 0.95, "text": " 2. V. K. Gupta, R. Mangla and S. Agarwal Pb() selective potentiometric sensor based on 4-tertbutycalx[4]arene in PVC matrix,\u201d Electroanalysis, vol. 14, p."}, {"category_id": 15, "poly": [145.0, 2037.0, 536.0, 2039.0, 536.0, 2074.0, 145.0, 2071.0], "score": 0.98, "text": "1127-1132, 2002. View at Google Scholar"}, {"category_id": 15, "poly": [113.0, 2069.0, 1555.0, 2069.0, 1555.0, 2103.0, 113.0, 2103.0], "score": 0.96, "text": " 3. V. K. Gupta, P. J. M. Carrott, M. M. L. Ribeiro Carrott, and S. Suhas, \u201cLow-cost adsorbents: growing approach to wastewater treatment a review,' Critical"}, {"category_id": 15, "poly": [113.0, 2127.0, 1496.0, 2127.0, 1496.0, 2159.0, 113.0, 2159.0], "score": 0.98, "text": "4. V. K. Gupta, R. N. Goyal, and R. A. Sharma, \u201cNovel PVC membrane based alizarin sensor and its application; determination of vanadium, zirconium and"}, {"category_id": 15, "poly": [145.0, 2156.0, 1422.0, 2156.0, 1422.0, 2190.0, 145.0, 2190.0], "score": 0.99, "text": "molybdenum\" International Journal of Electrochemical Science, vol. 4, no. 1, pp. 156-172, 2009. View at Google Scholar View at Scopus"}, {"category_id": 15, "poly": [111.0, 2181.0, 1557.0, 2186.0, 1557.0, 2220.0, 111.0, 2215.0], "score": 0.98, "text": " 5. A. K. Jain, V. K. Gupta, B. B. Sahoo, and L. P. Singh, \u201cCopper(Ml)-selective electrodes based on macrocyclic compounds,\u201d Analytical Proceedings including"}, {"category_id": 15, "poly": [148.0, 2215.0, 1262.0, 2215.0, 1262.0, 2249.0, 148.0, 2249.0], "score": 0.98, "text": "Analytical Communications, vol 32, no. 3, pp. 99-101, 1995. View at Publisher View at Google Scholar \u00b7 View at Scopus"}, {"category_id": 15, "poly": [462.0, 280.0, 1557.0, 283.0, 1557.0, 317.0, 462.0, 314.0], "score": 0.98, "text": "values decrease as temperature rises, confrming that the rate of biosorption is faster at lower temperatures, which is probably"}, {"category_id": 15, "poly": [89.0, 1481.0, 264.0, 1481.0, 264.0, 1513.0, 89.0, 1513.0], "score": 0.98, "text": "Figure 7: Plot of ln"}, {"category_id": 15, "poly": [89.0, 1172.0, 469.0, 1172.0, 469.0, 1206.0, 89.0, 1206.0], "score": 0.97, "text": "distribution coeffcient of the adsorbate and"}, {"category_id": 15, "poly": [494.0, 1172.0, 532.0, 1172.0, 532.0, 1206.0, 494.0, 1206.0], "score": 1.0, "text": "and"}, {"category_id": 15, "poly": [89.0, 397.0, 517.0, 397.0, 517.0, 431.0, 89.0, 431.0], "score": 0.95, "text": "Elovich equation disagreed with the experimental"}, {"category_id": 15, "poly": [1378.0, 1133.0, 1444.0, 1138.0, 1444.0, 1172.0, 1377.0, 1167.0], "score": 1.0, "text": "where"}, {"category_id": 15, "poly": [1476.0, 1133.0, 1528.0, 1138.0, 1527.0, 1172.0, 1476.0, 1167.0], "score": 0.92, "text": "is the"}, {"category_id": 15, "poly": [1400.0, 1267.0, 1513.0, 1267.0, 1513.0, 1301.0, 1400.0, 1301.0], "score": 0.92, "text": " showed the"}, {"category_id": 15, "poly": [89.0, 855.0, 972.0, 850.0, 972.0, 884.0, 89.0, 889.0], "score": 0.97, "text": "Figure 6: The intraparticle diffusion plots for the adsorption ofNi) by GSA. (NilI) concentration,"}, {"category_id": 15, "poly": [91.0, 202.0, 1496.0, 202.0, 1496.0, 236.0, 91.0, 236.0], "score": 0.97, "text": "values of predicted equlbrium sorption capacities showed good agreement with the experimental equilbriumuptake values. Based on correlation coeffcients and"}, {"category_id": 15, "poly": [89.0, 1267.0, 1117.0, 1267.0, 1117.0, 1301.0, 89.0, 1301.0], "score": 0.97, "text": "spontaneous adsorption of Ni(ll) ions on GSA for the temperature range studied (298, 308 and 318 K). The negative"}, {"category_id": 15, "poly": [1165.0, 1267.0, 1220.0, 1267.0, 1220.0, 1301.0, 1165.0, 1301.0], "score": 0.96, "text": "value"}, {"category_id": 15, "poly": [86.0, 358.0, 127.0, 361.0, 127.0, 402.0, 86.0, 400.0], "score": 1.0, "text": "The"}, {"category_id": 15, "poly": [1312.0, 358.0, 1545.0, 361.0, 1545.0, 402.0, 1312.0, 400.0], "score": 0.99, "text": "values calculated fom the"}, {"category_id": 15, "poly": [1073.0, 1201.0, 1550.0, 1201.0, 1550.0, 1235.0, 1073.0, 1235.0], "score": 0.99, "text": "was obtained using (8) for different temperatures. The"}, {"category_id": 15, "poly": [303.0, 1481.0, 480.0, 1481.0, 480.0, 1513.0, 303.0, 1513.0], "score": 1.0, "text": "against temperature"}, {"category_id": 15, "poly": [536.0, 1481.0, 858.0, 1481.0, 858.0, 1513.0, 536.0, 1513.0], "score": 0.97, "text": "for the adsorption of Ni(Il) by GSA."}, {"category_id": 15, "poly": [91.0, 970.0, 538.0, 970.0, 538.0, 1004.0, 91.0, 1004.0], "score": 0.99, "text": "The thermodynamic parameters, Gibbs free energy"}, {"category_id": 15, "poly": [596.0, 970.0, 686.0, 970.0, 686.0, 1004.0, 596.0, 1004.0], "score": 0.97, "text": ", enthalpy"}, {"category_id": 15, "poly": [89.0, 638.0, 790.0, 638.0, 790.0, 672.0, 89.0, 672.0], "score": 0.98, "text": "on to GSA at different temperature applied to diffusion model is shown in Figure"}, {"category_id": 15, "poly": [813.0, 638.0, 1503.0, 638.0, 1503.0, 672.0, 813.0, 672.0], "score": 0.96, "text": " and the intraparticle diffusion constants are given in Table 5. No plots of model"}, {"category_id": 15, "poly": [1400.0, 397.0, 1547.0, 397.0, 1547.0, 431.0, 1400.0, 431.0], "score": 0.99, "text": ", decreased with"}, {"category_id": 15, "poly": [683.0, 1233.0, 1022.0, 1233.0, 1022.0, 1267.0, 683.0, 1267.0], "score": 0.98, "text": " are negative (-8.5078, -8.0296, and"}, {"category_id": 15, "poly": [733.0, 1138.0, 1141.0, 1138.0, 1141.0, 1172.0, 733.0, 1172.0], "score": 0.98, "text": ") were calculated using the following equations:"}, {"category_id": 15, "poly": [562.0, 1172.0, 791.0, 1172.0, 791.0, 1206.0, 562.0, 1206.0], "score": 0.99, "text": "are as defined previously."}, {"category_id": 15, "poly": [812.0, 1172.0, 1515.0, 1172.0, 1515.0, 1206.0, 812.0, 1206.0], "score": 0.96, "text": "is the universal gas constant (8.314 J mol I K-1) and T is temperature (K) [27]."}, {"category_id": 15, "poly": [654.0, 1138.0, 694.0, 1138.0, 694.0, 1172.0, 654.0, 1172.0], "score": 1.0, "text": "and"}, {"category_id": 15, "poly": [91.0, 1138.0, 554.0, 1138.0, 554.0, 1172.0, 91.0, 1172.0], "score": 0.98, "text": "adsorption process. The thermodynamic parameters "}, {"category_id": 15, "poly": [599.0, 1138.0, 607.0, 1138.0, 607.0, 1172.0, 599.0, 1172.0], "score": 0.87, "text": "\uff0c"}, {"category_id": 15, "poly": [89.0, 1201.0, 655.0, 1201.0, 655.0, 1235.0, 89.0, 1235.0], "score": 0.96, "text": "and \u25b3S\u00b0 can be obtained from the slope and intercept of the plot"}, {"category_id": 15, "poly": [706.0, 1201.0, 1029.0, 1201.0, 1029.0, 1235.0, 706.0, 1235.0], "score": 0.96, "text": "against 1/T , respectively (Figure Z)."}, {"category_id": 15, "poly": [1185.0, 1233.0, 1338.0, 1233.0, 1338.0, 1267.0, 1185.0, 1267.0], "score": 1.0, "text": "at 298, 308, and"}, {"category_id": 15, "poly": [1399.0, 1233.0, 1560.0, 1233.0, 1560.0, 1267.0, 1399.0, 1267.0], "score": 0.98, "text": ", resp.), indicating"}, {"category_id": 15, "poly": [747.0, 970.0, 868.0, 970.0, 868.0, 1004.0, 747.0, 1004.0], "score": 0.99, "text": ", and entropy"}, {"category_id": 15, "poly": [919.0, 970.0, 1547.0, 970.0, 1547.0, 1004.0, 919.0, 1004.0], "score": 0.98, "text": "have an important role to determine spontaneity and heat change for the"}, {"category_id": 15, "poly": [91.0, 231.0, 1233.0, 231.0, 1233.0, 263.0, 91.0, 263.0], "score": 0.98, "text": "values calculated, it is evident that the adsorption of Ni(ll) can be best described by the pseudo-second-order kinetic model (Table"}, {"category_id": 15, "poly": [89.0, 1233.0, 206.0, 1233.0, 206.0, 1267.0, 89.0, 1267.0], "score": 1.0, "text": "data in Table"}, {"category_id": 15, "poly": [225.0, 1233.0, 631.0, 1233.0, 631.0, 1267.0, 225.0, 1267.0], "score": 0.98, "text": "showed that the standard free energy changes"}, {"category_id": 15, "poly": [1264.0, 397.0, 1308.0, 397.0, 1308.0, 431.0, 1264.0, 431.0], "score": 1.0, "text": "and"}, {"category_id": 15, "poly": [89.0, 314.0, 485.0, 314.0, 485.0, 346.0, 89.0, 346.0], "score": 0.98, "text": "due to a decrease in the interactions between"}, {"category_id": 15, "poly": [541.0, 314.0, 1323.0, 314.0, 1323.0, 346.0, 541.0, 346.0], "score": 0.99, "text": " ions and GSA as the biosorbent. This behavior is a characteristic of exothermic reactions."}, {"category_id": 15, "poly": [145.0, 1983.0, 546.0, 1983.0, 546.0, 2017.0, 145.0, 2017.0], "score": 0.98, "text": "no. 2, pp. 544-548, 2010. View at Publisher"}, {"category_id": 15, "poly": [562.0, 1983.0, 932.0, 1983.0, 932.0, 2017.0, 562.0, 2017.0], "score": 0.98, "text": "View at Google Scholar : View at Scopus"}, {"category_id": 15, "poly": [1351.0, 1065.0, 1385.0, 1065.0, 1385.0, 1092.0, 1351.0, 1092.0], "score": 0.99, "text": "(8)"}, {"category_id": 15, "poly": [541.0, 397.0, 1116.0, 397.0, 1116.0, 431.0, 541.0, 431.0], "score": 0.99, "text": "vales. It was observed that the Elovich model constants, namely,"}, {"category_id": 15, "poly": [1065.0, 855.0, 1177.0, 850.0, 1177.0, 884.0, 1065.0, 889.0], "score": 0.98, "text": ", GSA dose,"}, {"category_id": 15, "poly": [89.0, 280.0, 233.0, 283.0, 233.0, 317.0, 89.0, 314.0], "score": 0.98, "text": "Results of Table"}, {"category_id": 15, "poly": [252.0, 280.0, 435.0, 283.0, 435.0, 317.0, 252.0, 314.0], "score": 0.98, "text": "also showed that the"}, {"category_id": 15, "poly": [1047.0, 358.0, 1248.0, 361.0, 1248.0, 402.0, 1047.0, 400.0], "score": 0.98, "text": "for Elovich's equation."}, {"category_id": 15, "poly": [148.0, 2098.0, 1114.0, 2098.0, 1114.0, 2132.0, 148.0, 2132.0], "score": 0.97, "text": "Reviews in Environmental Science and Technology, vol. 39, no. 10, pp. 783-842, 2009. View at Publisher"}, {"category_id": 15, "poly": [1131.0, 2098.0, 1500.0, 2098.0, 1500.0, 2132.0, 1131.0, 2132.0], "score": 0.97, "text": "View at Google Scholar : View at Scopus"}, {"category_id": 15, "poly": [156.0, 358.0, 898.0, 361.0, 898.0, 402.0, 156.0, 400.0], "score": 0.95, "text": "values were in the range of0.484 to 0.926 for the various temperatures ranging fom"}, {"category_id": 15, "poly": [961.0, 358.0, 984.0, 361.0, 984.0, 402.0, 961.0, 400.0], "score": 0.6, "text": "10"}, {"category_id": 15, "poly": [124.0, 609.0, 1442.0, 612.0, 1442.0, 646.0, 124.0, 643.0], "score": 0.97, "text": " indicates the thickness of the boundary layer, that is larger values of I suggest greater boundary layer effects. The calculated data for the adsorption of"}, {"category_id": 15, "poly": [1499.0, 609.0, 1540.0, 612.0, 1540.0, 646.0, 1499.0, 643.0], "score": 1.0, "text": "ions"}], "page_info": {"page_no": 3, "height": 2339, "width": 1653}}, {"layout_dets": [{"category_id": 1, "poly": [104.688720703125, 78.35415649414062, 1568.3668212890625, 78.35415649414062, 1568.3668212890625, 1363.578369140625, 104.688720703125, 1363.578369140625], "score": 0.9997628927230835}, {"category_id": 13, "poly": [1113, 694, 1128, 694, 1128, 710, 1113, 710], "score": 0.42, "latex": "\\cdot"}, {"category_id": 13, "poly": [885, 695, 899, 695, 899, 710, 885, 710], "score": 0.42, "latex": "\\cdot"}, {"category_id": 13, "poly": [924, 753, 937, 753, 937, 769, 924, 769], "score": 0.41, "latex": "\\cdot"}, {"category_id": 13, "poly": [1152, 753, 1167, 753, 1167, 769, 1152, 769], "score": 0.37, "latex": "\\cdot"}, {"category_id": 13, "poly": [231, 1101, 245, 1101, 245, 1117, 231, 1117], "score": 0.36, "latex": "\\cdot"}, {"category_id": 13, "poly": [1054, 230, 1069, 230, 1069, 245, 1054, 245], "score": 0.34, "latex": "\\cdot"}, {"category_id": 13, "poly": [926, 288, 941, 288, 941, 304, 926, 304], "score": 0.34, "latex": "\\cdot"}, {"category_id": 13, "poly": [466, 1042, 480, 1042, 480, 1058, 466, 1058], "score": 0.32, "latex": "\\cdot"}, {"category_id": 13, "poly": [1163, 347, 1178, 347, 1178, 362, 1163, 362], "score": 0.29, "latex": "\\cdot"}, {"category_id": 13, "poly": [1022, 1159, 1036, 1159, 1036, 1175, 1022, 1175], "score": 0.29, "latex": "\\cdot"}, {"category_id": 13, "poly": [1020, 1216, 1033, 1216, 1033, 1232, 1020, 1232], "score": 0.29, "latex": "\\cdot"}, {"category_id": 13, "poly": [594, 811, 607, 811, 607, 826, 594, 826], "score": 0.29, "latex": "\\cdot"}, {"category_id": 13, "poly": [1104, 173, 1118, 173, 1118, 188, 1104, 188], "score": 0.28, "latex": "\\cdot"}, {"category_id": 13, "poly": [460, 1101, 475, 1101, 475, 1117, 460, 1117], "score": 0.27, "latex": "\\cdot"}, {"category_id": 13, "poly": [409, 985, 423, 985, 423, 1000, 409, 1000], "score": 0.27, "latex": "\\cdot"}, {"category_id": 13, "poly": [1067, 463, 1081, 463, 1081, 478, 1067, 478], "score": 0.25, "latex": "\\cdot"}, {"category_id": 15, "poly": [111.0, 76.0, 1547.0, 78.0, 1547.0, 112.0, 111.0, 110.0], "score": 0.98, "text": " 6. 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# Characterization of severely deformed new composites fabricated by powder metallurgy including a stage of mechanical alloying
H. Ashuri, A. Hassani*<br>Faculty of Materials Science and Engineering, Semnan University, Semnan 35131-19111, Iran
## ARTICLE INFO
## Article history:
Received 11 February 2014
Received in revised form 11 June 2014
Accepted 4 August 2014
Available online 12 August 2014
## Keywords:
Nanocomposite
Mechanical alloying
Twist extrusion
Powder metallurgy
#### Abstract
Mechanical properties of new composites having a binary matrix of $\mathrm{Al}-4 \mathrm{Cu}$ reinforced with $\mathrm{TiO}_{2}$ nano particles were investigated. The composites which consisted of $2 \mathrm{wt} \%$ and $8 \mathrm{wt} \%$ of $\mathrm{TiO}_{2}$ reinforcement particles, were fabricated using mechanical alloying and a powder metallurgy route. Morphology, phases and compounds formed during ball milling and densification of samples were studied. With increasing percentages of the reinforcement particles, mechanical properties of the composites were enhanced. Microstructural evolution and mechanical properties changes of the composites after application of twist extrusion (TE), as a severe plastic deformation (SPD) process, were also investigated. It was revealed that the more TE passes the higher hardness and yield strength obtained. In addition, increasing TE passes, led to occurrence of a more homogeneous distribution of the reinforcement particles within the structure, and development of an ultrafine-grained nano-structure. The maximum allowable number of TE passes was found to be four, above which the materials failed.
## 1. Introduction
In recent decades, aluminum matrix composites (AMC) with discontinuous reinforcements have vastly been attracted by different industries due to their good mechanical properties. Large number of manufacture routes have been developed to produce these materials among which powder metallurgy (PM) routes have been more considered with several causes. First, in powder metallurgy a controlled phase microstructure can be achieved. On the other hand, lower temperatures used in PM processes make the interphase kinetics be precisely controlled. In PM routes, the powders of elements and alloys are used which might be more inexpensive, and of course, much more effective in reinforcement of the composites. Traditional stages of PM-AMCs fabrication include mixing and blending the powders; degassing the solidified product in vacuum; homogenizing through hot pressing or hot isostatic pressing (HIP) [1].
AMCs are widely used in automotive, aerospace and transport industries because of their light weight, high elastic modulus, improved strength and good wear resistance. Strength and wear resistance of these materials are strongly dependent on volume fraction, size and type of reinforcement particles. They are well established that compared to their un-reinforced matrix alloys show higher wear resistance. AMCs with ceramic particles including $\mathrm{SiC}, \mathrm{TiC}, \mathrm{C}_{4} \mathrm{~B}, \mathrm{TiB}_{2}$ and $\mathrm{Al}_{2} \mathrm{O}_{3}$ are relatively easy to process and, in comparison with fiber-reinforced composites, are nearly isotropic [2].
Particulate AMCs have introduced most wide spread applications and hold the greatest promise for future growth because of their tailored properties, low cost-effectiveness and high volume production methods [3]. Aluminum matrix composites are known to be hard materials exhibiting a low forming capacity through the conventional techniques. Nevertheless, many promising attempts have been made to produce Al composites with a high potential of being formed plastically and even superplastically while their strength is retained [4].
Mechanical alloying (MA) is an interesting powder metallurgy route for producing of powders with high homogeneity and uniformity. This technique is very effective in dispersion of reinforcement particles and enhances grain refinement, which induces an increase of strength and hardness [5].
In recent years, manifestation of severe plastic deformation (SPD) methods in material science has shed light on new prospects in achieving a unique combination of high strength and ductility [6] as well as attaining ultrafine-grained materials with improved properties. SPD is a family of metal forming techniques that use extensive hydrostatic pressure to impose a very high strain on bulk solids, producing exceptional grain refinement without introducing any significant change in the overall dimensions of the sample[7]. Several different SPD techniques are now available; these include high-pressure torsion (HPT) [8], equal channel angular pressing (ECAP) [9], multi-directional forging (MDF) [10], accumulative roll-bonding (ARB) [11], repetitive corrugation and strengthening (RCS) [12], spread extrusion (SE) [13], simple shear extrusion (SSE) [14] and twist extrusion (TE) [15,16]. The SPD products have much higher structural efficiency in comparison with their coarsegrained counterparts. However, high cost-effectiveness of most SPD methods is a central drawback to produce such materials in high quantities. Therefore, development of new SPD methods to tackle cost problem is important.
In 1999, Beygelzimer proposed a severe plastic deformation process that became known as Twist Extrusion (TE) [17]. This process can change the structure of materials, significantly improving some of their physical and mechanical properties and, even in certain cases, gaining new properties. TE works by extruding a prism specimen through a matrix whose profile consists of two prismlike regions separated by a twist passage. The extruded material undergoes an intense shift, with the properties that the final cross-section of the specimen is identical to the initial cross-section [18]. These properties allow for a repeated extrusion that accumulates the value of deformation. TE is carried out under high hydrostatic pressure in the center of deformation which is created by applying anti-pressure (back pressure) to the specimen when it exits the matrix. It is possible to produce more isotropic and homogeneous deformation by turning the samples $90^{\circ}$ in each consecutive deformation or alternatively, make the use of consecutive clockwise-anticlockwise-clockwise twists [19]. A comparison between TE and the two most widely used SPD methods, ECAE and HPT, reveals that firstly, TE provides some advantages over ECAE such as the ability to extrude the hollow parts and the rectangular cross-sections [6]. Secondly, HPT involves order of magnitude higher pressures than in any other SPD process which provides attainment of uniquely high strains and formation of ultrafine grained structures. From another point of view, twist extrusion that combines extrusion with torsion, was introduced to tackle the insufficiency of HPT, that is, its being limited to laboratory conditions due to small size of the samples [19]. There are currently three main application areas of TE: (a) obtaining ultrafine grained crystalline and nano-crystalline structures in bulk specimens, (b) increasing the plasticity of secondary non-ferrous metals and alloys, which allows one to significantly broaden the range of production, (c) obtaining bulk specimens by consolidating porous materials which allows one to create substantially different, new compositions with unique characteristics [20].
In TE, strain distribution along the cross-section of the specimen is inhomogeneous; getting away from the axe, plastic strain increases, thus, the grains being finer. The microstructural inhomogeneity leads to inhomogeneities in the mechanical properties of the composite; the central area of the cross section having lowest strength. It is expected that with increasing the number of TE cycles, the microstructure becomes uniform [21].
In the present study, a powder metallurgy route combined with mechanical alloying was employed to produce some particulate $\mathrm{Al}-\mathrm{Cu} / \mathrm{TiO}_{2}$ composites with low $\mathrm{TiO}_{2}$ contents. The products were then severely deformed by twist extrusion technique. The microstructures, densities, wear resistances, hardness and strengths of the resulted composites, in two different $\mathrm{TiO}_{2}$ reinforcement content of 2 and $8 \mathrm{wt} \%$ and at various TE cycles were examined.
## 2. Experimental procedures
To attain a uniform distribution of the $\mathrm{TiO}_{2}$ reinforcement particles in $\mathrm{Al}-\mathrm{Cu}$ matrix, a high-energy planetary ball-mill machine, manufactured by the authors was utilized and, the powder behavior was studied during the process. Milling time and the effects of volume fraction of the reinforcement and its particle size were also investigated. Aluminum powder with mean grain size of $<45 \mu \mathrm{m}$ and commercial purity of $99.9 \%$ and copper powder of $40 \mu \mathrm{m}$ with $99.0 \%$ purity were supplied. Nano-scale anatase $\mathrm{TiO}_{2}$ powder, as the reinforcement, having a mean size of $50 \mathrm{~nm}$ was also obtained. The powders specifications are shown in Table 1.
The appropriate proportions of $\mathrm{Al}$ and $\mathrm{Cu}$ powders were weighed using a digital balance of $0.001 \mathrm{mg}$ accuracy. Internal surfaces of the cups were wetted with a thin layer of glycerin to prevent sticking the powders mixtures on them. The powders were then mixed and blended in a high energy planetary ball mill to produce the matrix alloy powder. For ball-milling, chromium steel balls with diameters of 17 , $19,22,25$ and $30 \mathrm{~mm}$, ball-to-powder weight ratio of $20: 1$, constant rotational speed of $300 \mathrm{rpm}$ and argon atmosphere were used. Ball milling time was $16 \mathrm{~h}$. To reinforce the product, $2 \mathrm{wt} \%$ and $8 \mathrm{wt} \%$ of $\mathrm{TiO}_{2}$ particles were added and blended to a homogeneous mixture. The mixture was cold compacted into a two-piece die of DIN-1.2344 hot die steel having a hole of $15 \times 15 \times 80 \mathrm{~mm}$ dimensions for $15 \mathrm{~min}$ under $600 \mathrm{MPa}$. Then, to enhance apparent densities of powders, they were put into the die under $100 \mathrm{MPa}$ pressure being heated to temperatures of $550^{\circ} \mathrm{C}, 580^{\circ} \mathrm{C}$ and $640^{\circ} \mathrm{C}$. After reaching these temperatures, the pressure was turned up to $700 \mathrm{MPa}$ at which the samples were kept for 30,60 and $120 \mathrm{~min}$ to obtain three different densities. After sintering, the samples were furnace cooled and homogenized to room temperature at a rate of $21.8^{\circ} \mathrm{C} / \mathrm{h}$.
For twist extrusion testing, the samples were lubricated with $\mathrm{MoS}_{2}$ to reduce friction. Then, they were inserted into the entrance guide of the twist extrusion die being pushed to the distorted channel using a steel plunger with speed of $1.1 \mathrm{~mm} / \mathrm{s}$. The twist extrusion die of $14.6 \times 14.6 \mathrm{~mm}$ internal cross-section with a twist line slope of $\beta=60^{\circ}$ in the counter-clockwise direction was used (Fig. 1). In order to apply a backpressure on the sample, the output channel was built steeped. This channel, itself, acted as a direct extrusion die. Thus, after the specimen passes the twisted channel, enters a straight output passage of $29 \mathrm{~mm}$ length during which its cross-section changed from $14.6 \times 14.6 \mathrm{~mm}$ to $14.2 \times 14.2 \mathrm{~mm}$. In addition, for preventing deviation of the sample to the sides and making sure of upright entering of the sample into the twisted channel, an $80 \mathrm{~mm}$ channel with $15 \times 15 \mathrm{~mm}$ crosssection was developed at the entrance as the sample guide. Also, to inhibit stress concentration, the right angle corners of the die interior walls were blunted. In this research, two sets of $\mathrm{Al}-4 \mathrm{wt} \% \mathrm{Cu} / 2 \mathrm{wt} \% \mathrm{TiO}_{2}$ and $\mathrm{Al}-4 \mathrm{wt} \% \mathrm{Cu} / 8 \mathrm{wt} \% \mathrm{TiO}_{2}$ samples were extruded at velocity of $68.4 \mathrm{~mm} / \mathrm{min}$ (maximum velocity of the available press) for 1,2 and 4 passes. The maximum allowed number of TE passes was found to be four, above which material failure occurred during twist extrusion operation.
To investigate the microstructure changes in the materials due to twist extrusion, the samples were prepared by cutting from the cross-section perpendicular to the axial direction of the extruded billets. The microstructure evolution was then studied in the central, lateral and corner regions of the cross-section using scanning electron microscopy (SEM).
Densities of the compacted powders were determined through Archimedes procedure according to the standard ASTM B93-13 [22]. The microstructures of samples from both composites were studied using SEM model ISI ABT SR-50 equipped with EDX analyzer after their preparation including grinding, polishing and etching with Keller etchant solution. To investigate the formation of deleterious phases like $\mathrm{Al}_{7} \mathrm{Cu}_{2} \mathrm{Fe}$ and $\mathrm{Al}_{4} \mathrm{C}_{3}, \mathrm{X}$-ray diffraction examinations and scanning electron microscopy observations were carried out on the sintered composites. To evaluate grain size and lattice strain, spectroscope system equipped with copper ray lamp (wavelength $1.5405 \AA$ ) was utilized. Williamson-Hall equation was used to determine crystallite size and lattice strain in diffracting domain. For hardness measurements of the sintered samples, Vickers hardness testing machine with the applied force of $1000 \mathrm{~g}$ was utilized.
To evaluate wear resistance of the composite specimens, tribological studies were conducted according to ASTM G99-04 standard [23] using a WAZAU pin-ondisk wear testing machine connected to computer interface from Tribo V4.3L software. The samples were cut from the cross-section perpendicular to the extrusion direction. Hardness testing was performed on the points across cross-section diameter with $1 \mathrm{~mm}$ intervals from one corner to the other. The samples were cut by a Merck lathe from the upper part of the cylindrical samples to make disks of $50 \mathrm{~mm}$ diameter and $4 \mathrm{~mm}$ thickness. To polish the sample surfaces, they were ground against 100,200 , and 500 grit emery papers. As the wearing apparatus, pins of $5 \mathrm{~mm}$ length and $2 \mathrm{~mm}$ diameter from 2160 steel with 60 HRC were prepared. The applied force and sliding distance were selected to be $30 \mathrm{~N}$ and $1000 \mathrm{~m}$, respectively. Wear coefficient, K, was predicted using the Archard equation [24]:
$V=K W L / H$
where $V$ is the lost volume of the worn material, $H$ Brinell hardness, $W$ normal applied load equal to $30 \mathrm{~N}, L$ the sliding distance (m) and $K$ wear coefficient.
Table 1
Specifications of powders used in this study.
| Powder | Particle size | Purity (\%) |
| :--- | :--- | :--- |
| $\mathrm{Al}$ | $<45 \mu \mathrm{m}$ | 99.9 |
| $\mathrm{Cu}$ | $<40 \mu \mathrm{m}$ | 99 |
| $\mathrm{TiO}_{2}$ | $<50 \mathrm{~nm}$ | 99 |
Fig. 1. Twist channel of TE die with $\alpha=90^{\circ}$ and $\beta=60^{\circ}$.
To investigate mechanical properties of the composites and to plot true stresstrue strain relation, compression tests were carried out. The cylindrical compression samples were cut from the centre of the billets for 1,2 and 4 cycles with ratio of $H / D=1$, separately out of the samples containing 2 and $8 \mathrm{wt} \% \mathrm{TiO}_{2}$ and, then were prepared and polished. The tests were conducted at ambient temperature. True stress-true strain relation of samples in each pass were inferred from compressive stress-strain curves.
## 3. Results and discussion
### 3.1. Powders specifications
Firstly, to determine the adequate milling duration, aluminum powder and $4 \mathrm{wt} \% \mathrm{Cu}$ powder were mixed and ball-milled for 5, 6 and $8 \mathrm{~h}$. The XRD patterns are compared in Fig. 2a. As seen, with increasing the milling time, the XRD peak intensities for aluminum and copper phases decreased and the XRD peak intensity of $\mathrm{Al}_{2} \mathrm{Cu}$ phase increased, therefore, it is inferred that after $8 \mathrm{~h}$ milling, the phase $\mathrm{Al}_{2} \mathrm{Cu}$ was formed and alloying process was completed.Now, $2 \mathrm{wt} \% \mathrm{TiO}_{2}$ reinforcement powder was added to the mixture and milled for 4 more hours (two-stage alloying). Next, aluminum, copper and $\mathrm{TiO}_{2}$ powders were mixed together and were milled in two portions for 12 and $16 \mathrm{~h}$ (one-stage alloying). Compressive results are shown in Fig. 2b. In two-stage conditions, as observed in Table 2, the subgrain size is smaller, but formation of $\mathrm{Al}_{7} \mathrm{Cu}_{2} \mathrm{Fe}$ brittle phase occurred that might be due to gradual intrusion of $\mathrm{Fe}$ into the mixture during ball-milling through surface erosion of the balls and cups. On the other hand, the weak signs of the formation of that phase were observed in one-stage milling for $16 \mathrm{~h}$. Therefore, to minimize the possible formation of the deleterious brittle phase of $\mathrm{Al}_{7} \mathrm{Cu}_{2} \mathrm{Fe}$ in the final product, all samples were produced through one-stage, $16 \mathrm{~h}$ ball-milling. In Fig. 2c, the results of X-ray diffraction experiments for milling of $\mathrm{Al}-4 \mathrm{wt} \% \mathrm{Cu}$ powder mixture containing $8 \mathrm{wt} \% \mathrm{TiO}_{2}$ for $16 \mathrm{~h}$ are depicted. The results indicated the formation of $\mathrm{Al}_{2} \mathrm{Cu}$ phase which witnesses that the alloying was performed successfully. The deleterious brittle phase of $\mathrm{Al}_{7} \mathrm{Cu}_{2} \mathrm{Fe}$ was not observed in the final product.
Fig. 2. XRD results (a) for different milling times of Al-4Cu, (b) comparison of results for $12 \mathrm{~h} 2$-stage with $12 \mathrm{~h}$ and $16 \mathrm{~h} 1$-stage mechanical alloying and (c) for $16 \mathrm{~h}$ milling of powder mixture containing $8 \mathrm{wt} \% \mathrm{TiO}_{2}$.
Table 2
A comparison of subgrain size and grain strain in different milling times.
| Sample | Type of milling | Milling time $(\mathrm{h})$ | Subgrain size $(\mathrm{nm})$ | Grain strain |
| :--- | :--- | :--- | :--- | :--- |
| $\mathrm{Al}-4 \mathrm{Cu} / 2 \mathrm{TiO}_{2}$ | Two stage | 12 | 11 | 0.0017 |
| $\mathrm{Al}-4 \mathrm{Cu} / 2 \mathrm{TiO}_{2}$ | One stage | 12 | 33 | 0.0045 |
| $\mathrm{Al}-4 \mathrm{Cu} / 2 \mathrm{TiO}_{2}$ | One stage | 16 | 31.51 | 0.00475 |
| $\mathrm{Al}-4 \mathrm{Cu} / 8 \mathrm{TiO}_{2}$ | One stage | 16 | 28.41 | 0.00481 |
Table 3
Relative densities of samples at 700 Mpa pressure for $30 \mathrm{~min}$ at different temperatures.
| Sample | Theoretical density $\left(\mathrm{g} / \mathrm{cm}^{3}\right)$ | Bulk density $\left(\mathrm{g} / \mathrm{cm}^{3}\right)$ | Temperature $\left({ }^{\circ} \mathrm{C}\right)$ | Relative density $(\%)$ | Porosity percentage $(\%)$ |
| :--- | :--- | :---: | :--- | :--- | :--- |
| $\mathrm{Al}-4 \mathrm{Cu} / 2 \mathrm{TiO}_{2}$ | 2.797 | $2.256 \pm 0.0006$ | 550 | 90.31 | 9.69 |
| | | $2.7095 \pm 0.0004$ | 580 | 96.87 | 3.13 |
| $\mathrm{Al}-4 \mathrm{Cu} / 8 \mathrm{TiO}_{2}$ | 2.856 | $2.7452 \pm 0.003$ | 640 | 98.15 | 1.85 |
| | | $2.759 \pm 0.004$ | 640 | 98.64 | 1.36 |
### 3.2. Evaluation of composites
For hot compacting, the twist extruded samples having $2 \mathrm{wt} \% \mathrm{TiO}_{2}$, first, temperature of $550^{\circ} \mathrm{C}$ and, then $580{ }^{\circ} \mathrm{C}$ were applied. Densities of those samples were calculated using dipping-in-water procedure (Eqs. (2) and (3)) and, since their measured densities at above two temperatures were found to be very low ( $<97 \%)$, higher temperatures were applied. The applied pressure for all samples was fixed at $700 \mathrm{MPa}$ for $30 \mathrm{~min}$. Porosity volume fraction was also determined using Eq. (3); the results are presented in Table 3. For applying a uniform axial pressure, the ratio of height to diameter $(h / d)$ was about 1.5 .
$\rho=\frac{W_{\text {air }}\left\lfloor\rho_{\text {water }}-0.0012\right\rfloor}{0.99983\left\lfloor W_{\text {air }}-W_{\text {water }}\right\rfloor}+0.0012$
$\rho_{T}=\sum_{i=1}^{n} f_{i} \rho_{i}$
$\%$ Porosity $=\frac{\rho_{T}-\rho}{\rho_{T}} \times 100$
where $W_{\text {air }}$ is the measured weight of the sample in air, $W_{\text {water }}$ the weight in water, $\rho$ measured density, $\rho_{\text {water }}$ density in water, $\rho_{T}$ theoretical density.In hot compression test performed on composite, temperature of $640^{\circ} \mathrm{C}$ was applied for the other samples, but their holding time in the furnace increased to 60 and $120 \mathrm{~min}$. The final densities are tabulated in Table 4. In hot compression situations at $640{ }^{\circ} \mathrm{C}$ for $120 \mathrm{~min}$, the density of the sintered sample was nearly equal to the theoretical density of the composite. Therefore, the same conditions were repeated for the mixture powder containing $8 \mathrm{wt} \% \mathrm{TiO}_{2}$ reinforcement. Because the density of $\mathrm{TiO}_{2}$ particles was higher than that of the matrix alloy $\left(4.5 \mathrm{~g} / \mathrm{cm}^{3}\right)$, it was anticipated that with increasing volume fraction of reinforcement particles, the relative density of the composite increased [5] which was consistent with the results depicted in Table 4.
Fig. 4. SEM micrograph of sample $\mathrm{Al}-4 \mathrm{Cu} / 8 \mathrm{wt} \% \mathrm{TiO}_{2}$ showing large agglomerated $\mathrm{TiO}_{2}$ particles.
Table 4
Relative densities of samples at $700 \mathrm{MPa}$ pressure at $640^{\circ} \mathrm{C}$ and different times.
| Sample | Theoretical density $\left(\mathrm{g} / \mathrm{cm}^{3}\right)$ | Bulk density $\left(\mathrm{g} / \mathrm{cm}^{3}\right)$ | Time $(\mathrm{min})$ | Relative density $(\%)$ | Porosity percentage $(\%)$ |
| :--- | :--- | :--- | :--- | :--- | :--- |
| $\mathrm{Al}-4 \mathrm{Cu} / 2 \mathrm{TiO}_{2}$ | 2.797 | $2.252 \pm 0.0008$ | 30 | 98.15 | 1.85 |
| | | $2.757 \pm 0.0005$ | 60 | 98.59 | 1.41 |
| $\mathrm{Al}-4 \mathrm{Cu} / 8 \mathrm{TiO}_{2}$ | 2.856 | $2.769 \pm 0.0003$ | 120 | 99.01 | 0.99 |
| | | $2.833 \pm 0.0004$ | 120 | 99.20 | 0.80 |
Fig. 3. SEM images of samples reinforced with (a) 2 and (b) $8 \mathrm{wt} \% \mathrm{TiO}_{2}$ particles prior to $\mathrm{TE}$.
Fig. 5. (a and b) XRD patterns of composites reinforced with $2 \mathrm{wt} \% \mathrm{TiO}_{2}$ and $8 \mathrm{wt} \% \mathrm{TiO}_{2}$ nano-particles and (c and d) EDX analysis results for those composites, respectively.
Table 5
Weight percentage of elements in $\mathrm{Al}-4 \mathrm{Cu} / 2 \mathrm{wt} \% \mathrm{TiO}_{2}$ and $\mathrm{Al}-4 \mathrm{Cu} / 8 \mathrm{wt} \% \mathrm{TiO}_{2}$ derived from EDX analysis.
| Element | wt\% of element in $\mathrm{Al}-4 \mathrm{Cu} /$ <br> $2 \mathrm{wt} \% \mathrm{TiO}_{2}$ | wt\% of element in $\mathrm{Al}-4 \mathrm{Cu} /$ <br> $8 \mathrm{wt} \% \mathrm{TiO}_{2}$ |
| :---: | :---: | :---: |
| $\mathrm{Al}$ | 84.1 | 77.14 |
| $\mathrm{Cu}$ | 3.88 | 3.68 |
| $\mathrm{Ti}$ | 2.08 | 7.86 |
| 0 | 9.94 | 11.32 |
| Total | 100 | 100 |
Fig. 3 shows SEM micrographs of the samples containing $2 \mathrm{wt} \% \mathrm{TiO}_{2}$ and $8 \mathrm{wt} \% \mathrm{TiO}_{2}$ prior to TE with coarse distinct grains. As seen, the reinforcement particles are distributed uniformly within the matrix. The particles became finer with smooth edges and corners during ball-milling. Uniform distribution of nanoparticles within matrix, because of their high surface to volume ratio, is difficult. In the composites with $8 \mathrm{wt} \% \mathrm{TiO}_{2}$, distribution of these nano-particles was inhomogeneous resulting in formation of their large agglomerates; these usually impair mechanical properties of materials. This is more evident in Fig. 4.
Fig. 6. (a) $\mathrm{SE}$ images of composite reinforced with $2 \mathrm{wt} \% \mathrm{TiO}_{2}$ and $\mathrm{EDX}$ analysis of point $\mathrm{A}$ and $\mathrm{B}$, (b) $\mathrm{SE}$ micrograph of composite reinforced with 8 wt $\% \mathrm{TiO}_{2}$ with $\mathrm{EDX}$ analysis of points $A$ and $B$.
Fig. 7. Compression true stress-true strain curves for annealed samples until beginning of barreling.
According to XRD results shown in Fig. 5a, presence of the brittle phase (i.e. $\mathrm{Al}_{7} \mathrm{Cu}_{2} \mathrm{Fe}$ in the sintered $\mathrm{Al}-4 \mathrm{Cu} / 2 \mathrm{TiO}_{2}$ sample, which causes brittle fracture of the material, is confirmed. However, X-ray diffraction pattern in Fig. $5 \mathrm{~b}$ indicates that in the $\mathrm{Al}-4 \mathrm{Cu} / 8 \mathrm{TiO}_{2}$ sample, the brittle phase is absent. In the next stages of experiments, it will be noticed that with application of severe plastic strains, fracture of latter samples occurred more frequently in comparison with the former ones. For performing quantitative analysis of the existing elements in the samples, EDX was utilized. The results are depicted in Fig. 5(c) and (d) as well as in Table 5. Those results were obtained from surfaces of the samples showing the total weight percentage of the elements in the sintered samples. The analysis showed no contamination.
Fig. 6(a) shows secondary electron (SE) micrograph of a sample with composition of $\mathrm{Al}-4 \mathrm{Cu} / 2 \mathrm{TiO}_{2}$ together with $\mathrm{EDX}$ analyses of points A and B (specified with circles), which are nearly identical. Therefore, it is concluded that the reinforcing particles are uniformly distributed within the matrix, as mentioned earlier. However, EDX analyses of points A and B of SE micrograph of the sample $\mathrm{Al}-4 \mathrm{Cu} / 8 \mathrm{TiO}_{2}$ shown in Fig. 6 (b) are quite dissimilar. It means that a non-uniform distribution of $\mathrm{TiO}_{2}$ nano-particles coupled with their large agglomerates, which usually contribute to deterioration of mechanical properties of the composite, occurred.
Compression true stress-true strain curves of the annealed samples, in the case of $\mathrm{Al}-4 \mathrm{Cu}, \mathrm{Al}-4 \mathrm{Cu} / 2 \mathrm{wt} \% \mathrm{TiO}_{2}$ and $\mathrm{Al}-4 \mathrm{Cu} /$ $8 \mathrm{wt} \% \mathrm{TiO}_{2}$ are illustrated and compared in Fig. 7 and the results are shown in Table 6. It is evident that with increasing $\mathrm{TiO}_{2}$ content in the composite, yield stress and Young modulus increase but, ductility decreases. Perhaps, deletion of porosities during hot compression at $640^{\circ} \mathrm{C}$ for $120 \mathrm{~min}$ was effective in enhancement of the sample strength. On the other hand, $\mathrm{TiO}_{2}$ particles are stable thermodynamically, and do not react with the matrix phase at high temperatures. These particles act as barriers against movement of dislocations leading to ductility decrease [25].
Fig. 8 shows variation of lost volume of composites during wear test vs. sliding distance. As previously shown, with increasing the percentage of $\mathrm{TiO}_{2}$ reinforcement, the lost volume decreases. To predict wear coefficient, Eq. (1) was used. The graph in Fig. 9 shows variation of wear coefficient with sliding distance for all samples. As indicated, the lowest wear coefficient belongs to the composite having $8 \mathrm{wt} \% \mathrm{TiO}_{2}$. It is also evident in Table 7 that with increasing weight percentage of $\mathrm{TiO}_{2}$ particles, the hardness of the material increases. Such a hardness increasing can be attributed to the increasing of dislocation densities improving material resistance. Hardness increasing leads to enhancement of wear resistance of the composite [25].
Fig. 8. Variation of lost volume of matrix alloy and composite vs. sliding distance in wear test.
Fig. 9. Variation of wear coefficient for matrix alloy and composites vs. sliding distance at pressure of $30 \mathrm{~N}$.
Table 7
Mean Brinell hardness for different samples.
| Specimen | Hardness (Brinell) |
| :--- | :--- |
| $\mathrm{Al}-4 \mathrm{Cu}$ | 107 |
| $\mathrm{Al}-4 \mathrm{Cu} / 2 \mathrm{TiO}_{2}$ | 138 |
| $\mathrm{Al}-4 \mathrm{Cu} / 8 \mathrm{TiO}_{2}$ | 200 |
Fig. 10 are the backscattered electron BSE images of samples $\mathrm{Al}-4 \mathrm{Cu} / 2 \mathrm{wt} \% \mathrm{TiO}_{2}$ and $\mathrm{Al}-4 \mathrm{Cu} / 8 \mathrm{wt} \% \mathrm{TiO}_{2}$ from central and lateral regions. EDX examinations revealed that the two discrete dark and light regions corresponding to $\mathrm{TiO}_{2}$ clusters and the matrix, respectively. Fig. 10(a), (b), (e) and (f) shows the microstructure of two composites in central area after two passes and four passes of twist extrusion, respectively. It is revealed that grains became finer and the microstructure was more uniform with increasing the number of TE passes and this is same for Fig. 10(c), (d), (g) and (h) that illustrate the microstructure of lateral region of cross-section of both composites after two passes and four passes of TE, respectively. After four passes of TE in both composites, formation of nano-sized grains are evident. Unlike significant effect of billet axial rotations between ECAP passes [26,27], the billet rotations between TE passes have no effect on the plastic flow. This is due to the axial symmetry of the process.
Table 6
Results of uniaxial compression testing for annealed samples.
| Specimen | Young modulus (GPa) | Yield strength (GPa) | Barreling stress (MPa) | Barreling strain (\%) |
| :--- | :--- | :--- | :--- | :--- |
| $\mathrm{Al}-4 \mathrm{Cu}$ | 66 | 256 | 270 | 0.96 |
| $\mathrm{Al}-4 \mathrm{Cu} / 2 \mathrm{TiO}_{2}$ | 70 | 246 | 0.93 | 284|
| $\mathrm{Al}-4 \mathrm{Cu} / 8 \mathrm{TiO}_{2}$ | 79.6 | 278 | 284 | 0.87 |
Fig. 10. BSC images of composites, up: $\mathrm{Al}-4 \mathrm{Cu} / 2 \mathrm{wt} \% \mathrm{TiO}_{2}$ and down: $\mathrm{Al}-4 \mathrm{Cu} / 8 \mathrm{wt} \% \mathrm{TiO}_{2}$, (a, b, e and f) central regions, after 2 and 4 passes, (c, d, $\mathrm{g}$ and $\mathrm{h}$ ) lateral regions, after 2 and 4 passes.
Fig. 11. Grain size measurement for a corner of cross-section of a sample containing $8 \mathrm{wt} \% \mathrm{TiO}_{2}$ extruded for 2 passes.
Clustering of fine particles has been reported by Ritasalo et al. [28]. With increasing twist extrusion passes, $\mathrm{TiO}_{2}$ clusters became smaller having a more homogeneous distribution in the matrix. For the sample $\mathrm{Al}-4 \mathrm{Cu} / 8 \mathrm{wt} \% \mathrm{TiO}_{2}$, as observed, with increasing the number of TE passes, very fine equiaxed grains are formed. It is also evident that in the centre of the sample, the microstructure is less homogeneous and the formation of $\mathrm{TiO}_{2}$ clusters is observed. As indicated, in both types of samples, the microstructures in the corners and edges of the cross-section are more homogenous than those in the centers. This means that the corners experienced larger strains compared to the centre. In each pass of TE process, applying plastic deformation leads to an increase in dislocation density and, consequently formation of subgrains that impede dislocations glide gradually. With accumulation of plastic strains in subsequent passes, misorientation between neighboring grains increases and elongated grains turn to fine equiaxed ones resulting in a recrystallized microstructure [29]. This is the same phenomenon normally observed in SPD processes and is termed dynamic recrystallization [30].
Mishra et al. [29] suggested that when grains become smaller and also when the total area of grain boundaries increases, discrete dislocations emitted by a boundary are absorbed by the opposite grain boundary. Therefore, in higher passes of TE, dislocation density decreases gradually and high angle grain boundaries form. Shape of grains and rate of converting low angle boundaries to high angle ones in TE process depend on twist path and twist angle $(\alpha)$. It is worth noting that strain distribution and the boundary of deformation zones depend strongly on the geometry of die crosssection, i.e. deviation angle $(\beta)$ and twist angle $(\alpha)$, and by varying these factors, one can change strain intensity in different regions.
Grain sizes of the extruded samples were determined after each TE pass using a scaling-measuring utility installed to scanning electron microscope, as shown in Fig. 11 and the results are depicted in Table 8. It is inferred from Table 8 that with increasing TE passes, grain size in the centre and in the corners decreases. However, with increase of passes, the amount of strain that can be imposed on the sample, decreases. Such a decrease is further observed at edge regions. Therefore, uniformity of deformed structure increases and gradually, extent of grain refinement increases in central and lateral regions of the sample. This is due to structure stability brought about by saturation of the mechanical properties after the strain exceeds saturation limit. Such stability and saturation are not confined to TE, but are extended to all deformations based on pure shear like ECAP and so on. Mechanisms of this effect in PSD processes are such that with increasing passes (i.e. with increasing the strains), grain boundary surfaces also increase with a rate proportional to deformation state. During plastic deformation, cells or subgrains form and after a rather large strain, a considerable change does not occur in them. Therefore, with increasing strain, amount of high angle boundaries increases [29]. It is then concluded that with increasing the number of passes, the difference in grain sizes decreases in various regions of the sample. To determine extent of this difference in various passes, a variable index $(V)$ is defined as a ratio of standard deviation, SD to a parameter average value $\bar{x}$ as follows [31]:
$V=\frac{S D}{\bar{x}} \times 100$
Table 8
Mean grain size $(\mu \mathrm{m})$ of centers and corners of cross sections of two composites at various passes of TE.
| Sample | Position | Annealed | 1-pass | 2-pass | 4-pass |
| :--- | :--- | :--- | :--- | :--- | :--- |
| $\mathrm{Al}-4 \mathrm{Cu} / 2 \mathrm{wt} \% \mathrm{TiO}_{2}$ | Corner | $20.9 \mu \mathrm{m}$ | $11 \mu \mathrm{m}$ | $9 \mu \mathrm{m}$ | $7.1 \mu \mathrm{m}$ |
| | Center | $21.7 \mu \mathrm{m}$ | $20 \mu \mathrm{m}$ | $12 \mu \mathrm{m}$ | $8.4 \mu \mathrm{m}$ |
| $\mathrm{Al}-4 \mathrm{Cu} / 8 \mathrm{wt} \% \mathrm{TiO}_{2}$ | Corner | $18.2 \mu \mathrm{m}$ | $10 \mu \mathrm{m}$ | $7.8 \mu \mathrm{m}$ | $5.6 \mu \mathrm{m}$ |
| | Center | $18.8 \mu \mathrm{m}$ | $14 \mu \mathrm{m}$ | $9.8 \mu \mathrm{m}$ | $6.5 \mu \mathrm{m}$ |
Fig. 12. Grain size heterogeneity index for different passes for two composites.
Fig. 12 shows inhomogeneity of grain size for different passes and various $\mathrm{TiO}_{2}$ contents in composites. As indicated, the annealed sample is more homogeneous in grain size and, the sample extruded for one pass shows highest inhomogeneity. It is evident that with increasing the number of passes, the inhomogeneity of grain size decreases to a minimum of $V=\sim 16 \%$ for fourpass TE operation.
Fig. 13(a) shows the effect of $\mathrm{TiO}_{2}$ content on Vickers microhardness of the composites. A more uniform dispersion of $\mathrm{TiO}_{2}$ particle in the matrix impedes dislocation movements resulting in an increase of the hardness [32]. Fig. 13(b) and (c) shows the variation of hardness in the centre and corners of cross-section as well as mean hardness, in different passes of TE, for both types of composites. As seen, during first pass, the hardness increases dramatically, but in next passes, an obvious decrease in the curve slope is observed. This has been attributed to increase in dislocation density resulted from application of severe plastic deformation [29].Since corners get higher plastic strains than the centre, they possess higher hardness. However, with increasing the number of passes and gradual saturation of microstructure with strain due to saturation in dislocation density and, then development of a fine substructure, the heterogeneity in hardness distribution on the cross-section of the sample decreases. Therefore, despite occurrence of heterogeneity in deformation, hardness distribution is homogeneous at higher strains. Zendehdel et al. also reported homogeneity of hardness distribution at higher passes when they investigated influence of $\mathrm{TE}$ process on microstructure and mechanical properties of 6063 aluminum alloy [33]. Fig. 14(a) and (b) illustrates Vickers microhardness measured along diagonal line on cross-section of different samples. As indicated, hardness of samples increased noticeably after first pass compared to the annealed specimens. For the samples containing $2 \mathrm{wt} \% \mathrm{TiO}_{2}$, the hardness increased by $52 \%$ in average, but for the sample having $8 \mathrm{wt} \% \mathrm{TiO}_{2}$, the hardness increasing was $46 \%$. The hardness increase is lower for the central regions that undergoes lower strain levels and, higher for the lateral areas deformed by higher strains; this is due to higher redundant strains $\left(\varepsilon_{\mathrm{r}}\right)$ at the lateral regions [34]. The variation index, $V$, is also defined for description of heterogeneity level in hardness values. Using the variation index, $V$, calculated through Eq. (5) for different passes, Table 9 for the sample $\mathrm{Al}-4 \mathrm{Cu} / 2 \mathrm{wt} \% \mathrm{TiO}_{2}$ and Table 10 for the sample $\mathrm{Al}-4 \mathrm{Cu} / 8 \mathrm{wt} \% \mathrm{TiO}_{2}$ are tabulated. Fig. 15 shows the heterogeneity index of hardness values $(V)$ for different passes of TE. It is inferred from Tables 9 and 10, and Fig. 15 that, in addition to increase in hardness within the central and lateral areas, and also increasing average hardness in whole sample, heterogeneity increased as well. Hardness heterogeneity index value in the sample of $\mathrm{Al}-4 \mathrm{Cu} / 2 \mathrm{TiO}_{2}$ extruded for 4 passes reached to 8.44 from 1.37 for the conditions before TE and, also in the sample of $\mathrm{Al}-4 \mathrm{Cu} / 8 \mathrm{TiO}_{2}$ extruded for 4 passes, $V$ value reached to 12.45 from 1.42 for the conditions before TE. It seems that heterogeneous distribution of hardness within whole sample was not significant due to application of backpressure during the process. Because backpressure is necessary for completion of cinematic conditions of applied plastic flow through tool geometry of $\mathrm{TE}$, and facilitates development of more homogeneous structure and mechanical properties [30].
Fig. 13. (a) Variation of Vickers hardness of composites with different $\mathrm{TiO}_{2}$ contents, prior to TE. (b) Variation of hardness at central and lateral regions of cross-section and mean hardness at different $\mathrm{TE}$ passes for composite $\mathrm{Al}-4 \mathrm{Cu} / 2 \mathrm{wt} \% \mathrm{TiO}_{2}$. (c) Variation of hardness at central and lateral regions of cross-section and mean hardness at different TE passes for composite $\mathrm{Al}-4 \mathrm{Cu} / 8 \mathrm{wt} \% \mathrm{TiO}_{2}$.
Fig. 14. Vickers hardness measured along diagonal line over cross section of (a) sample $\mathrm{Al}-4 \mathrm{Cu} 8 \mathrm{wt} \% \mathrm{TiO}_{2}$ at various passes of $\mathrm{TE}$.
Fig. 15. Heterogeneity index of hardness values for various TE passes.
Table 9
Vickers microhardness values for samples $\mathrm{Al}-4 \mathrm{Cu} / 2 \mathrm{wt} \% \mathrm{TiO}_{2}$ at different passes and their heterogeneity values.
| Sample | Hardness in center (HV) | Mean hardness (HV) | Hardness of edge (HV) | Heterogeneity V (\%) |
| :--- | :--- | :--- | :--- | :--- |
| Annealed | 145 | 146 | 147 | 1.3 |
| 1-pass | 217 | 224 | 231 | 6.25 |
| 2-pass | 225 | 234 | 243 | 7.69 |
| 4-pass | 227 | 237 | 247 | 8.44 |
Table 10
Vickers microhardness values for samples $\mathrm{Al}-4 \mathrm{Cu} / 8 \mathrm{wt} \% \mathrm{TiO}_{2}$ at different passes and their heterogeneity values.
| Sample | Hardness in center (HV) | Mean hardness (HV) | Hardness of edge (HV) | Heterogeneity V (\%) |
| :--- | :--- | :--- | :--- | ---: |
| Annealed | 210 | 211.5 | 213 | 1.42 |
| 1-pass | 296 | 308.5 | 321 | 8.10 |
| 2-pass | 318 | 335.5 | 353 | 10.43 |
| 4-pass | 324 | 345.5 | 367 | 12.45 |
Fig. 16. Results of compression tests: (a) true stress-true strain curves for $\mathrm{Al}-4 \mathrm{Cu} / 2 \mathrm{wt} \% \mathrm{TiO}_{2}$, (b) true stress-true strain curves for $\mathrm{Al}-4 \mathrm{Cu} / 8 \mathrm{wt} \% \mathrm{TiO} \mathrm{O}_{2}$. (c) Variation of yield strength at different passes for both composites.
Table 11
Results of uniaxial compression testing on samples $\mathrm{Al}-4 \mathrm{Cu} / 2 \mathrm{wt} \% \mathrm{TiO}_{2}$ and $\mathrm{Al}-4 \mathrm{Cu} / 8 \mathrm{wt} \% \mathrm{TiO}_{2}$ (Type 1 and Type 2, respectively) at different passes.
<table><thead><tr><th rowspan="2">Sample</th><th colspan="2">Young modulus (GPa)</th><th colspan="2"> Yield strength (MPa)</th><th colspan="2">Barreling strain MPa</th><th colspan="2"> Barreling strain (%)</th></tr><tr><th>Type 1</th><th>Type 2</th><th>Type 1</th><th>Type 2</th><th>Type 1</th><th>Type 2</th><th>Type 1</th><th>Type 2</th></tr></thead><tr><td>Annealed</td><td>70</td><td>79.6</td><td>246</td><td>278</td><td>284</td><td>298</td><td> 0.93</td><td> 0.87</td></tr><tr><td>1-pass</td><td>84</td><td> 94.9</td><td> 304</td><td> 325</td><td>241</td><td>347</td><td>0.80</td><td>0.74</td></tr><tr><td>2-pass</td><td>85</td><td>96.6</td><td>334</td><td>354</td><td>358</td><td>366</td><td>0.66</td><td>0.62</td></tr><tr><td>4-pass</td><td>87.6</td><td>97.2</td><td>368</td><td>372</td><td>383</td><td>391</td><td>0.65</td><td>0.61</td></tr></table>
Fig. 16(a) and (b) shows graphs obtained from compression tests including true stres-true strain curves derived from uniaxial compression test on samples $\mathrm{Al}-4 \mathrm{Cu} / 2 \mathrm{wt} \% \mathrm{TiO}_{2}$ and $\mathrm{Al}-4 \mathrm{Cu} /$ $8 \mathrm{wt} \% \mathrm{TiO}_{2}$ after different TE passes, respectively. The obtained results are compared in Table 11. Fig. 16(c) illustrates variation curves of yield strength for both composites in different TE passes. As indicated, with increasing number of passes, strength increased and ductility decreased. The strength increase extent in the first pass is obviously higher than that in the second and fourth passes which is due to gradual strain saturation in different regions, particularly those closer to the centre. By applying a few number of TE passes, strain exceeds saturation limit and saturation state gradually extends all cross-section area leading to uniformity in changing microstructure and other properties [35].
## 4. Conclusions
Mechanical alloying and powder metallurgy routes were applied to fabricate a new composite with binary matrix of Al$4 \mathrm{Cu}$ and reinforced by $2 \mathrm{wt} \% \mathrm{TiO}_{2}$ nano-particles. The annealed materials were subjected to some of the mechanical tests, and hardness, strength and yield strength were measured. With increasing percentages of the reinforcement particles, hardness, yield strength, Young modulus and wear resistance of the composites increased but ductility decreased. Afterwards, the composites were deformed severely through twist extrusion for 1,2 and 4 passes. The maximum allowable passes of extrusion was four, beyond which the materials did not endure plastic deformation and failed. It was revealed that with increasing the number of passes by 4 , a more homogeneous distribution of reinforcement particles occurred and also an ultrafine-grained nano-structure was obtained.
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# Research Article
## The effects of AZD3582 [4-(nitroxy)butyl-(2S)-2-(6-methoxy-2naphthyl) propanoate], and naproxen on key pathogenic steps in NSAID-enteropathy in the rat.
M. Walley, G. Sigthorsson, C. Hotz-Behofsits, R. Simpson, I. Bjarnason*
Guy's, King's and St Thomas' School of Medicine, Department of Gastroenterology, King's College Hospital Foundation Trust, Denmark Hill,<br>London SE5 9PJ, London, UK, Tel: ++2032992417, Fax: ++2032996474, e-mail: ingvar.Bjarnason @kcl.ac.uk
Received 9 October 2006; revised 27 January 2007; accepted 1 February 2007
Abstract. Background: The pathogenesis of NSAID-induced enteropathy may involve dual inhibition of the cyclooxygenase (1 and 2 ) and a topical effect with sequential increased intestinal permeability, development of inflammation and ulcers. It has been suggested that nitric-oxide donating drugs cause significantly less gastrointestinal injury by counteracting for NSAID-induced reductions in blood flow.
Aims: To compare the effects of AZD3582 [4-(nitroxy)butyl(2S)-2-(6-methoxy-2-naphthyl) propanoate], and naproxen on key pathogenic steps in NSAID-enteropathy in the rat.
Methods: Single doses of AZD3582, naproxen (dose range $10-300 \mu \mathrm{mol} / \mathrm{kg}$ ) or vehicle were given to male Sprague Dawley rats. Intestinal permeability ( ${ }^{1} \mathrm{CrEDTA}$ ) and intestinal inflammation (granulocyte marker protein) was quantitated and ulcer counts made.
Results: Intestinal permeability (all doses) and inflammation (highest dose of the drugs) increased significantly from control levels following naproxen and AZD3582 and there was no significant difference between the drugs. Median ulcer counts were, however, significantly ( $\mathrm{p}<0.01$ ) lower with AZD3582 (4 $\pm 2$ ) than with naproxen $(17 \pm 4)$.
Conclusions: Naproxen and AZD3582 are equally associated with increased small intestinal permeability and inflammation, which is the consequence of their topical effect. The reduced small bowel ulcer counts with AZD3582 accords with the suggestion that vascular factors are the main driving force for NSAID-induced ulcer formation.
Key words: NSAIDs; CINODs; Nitric oxide; Naproxen; AZD3582[^0]
## Introduction
Nonsteroidal anti-inflammatory drugs (NSAIDs) cause gastrointestinal side effects which involve the stomach as well as the small bowel mucosa (Hawkey and Langman, 2003). Although the serious gastric side effects of bleeding and perforation have attracted the most attention, it is increasingly clear that the small bowel is associated with similar types and prevalence of complications (Bjarnason et al., 1993; Laine et al., 2002)
The pathogenesis of NSAID-induced gastrointestinal damage is uncertain. There is substantial evidence to suggest that NSAID-enteropathy in rodents is caused by various combinations of the selective biochemical effects of NSAIDs including cyclooxygenase (COX)-1 and COX-2 inhibition together with the topical effect (Somasundaram et al., 1995). The topical effect is thought to relate to the physicochemical properties of NSAIDs to act as detergents (Lichtenberger et al., 1995) and uncouplers of mitochondrial oxidative phosphorylation (Somasundaram et al., 1995). Collectively, it is suggested that the topical effect results in increased intestinal permeability with mucosal exposure of luminal aggressive factors and hence inflammation. It is also suggested that NSAID-induced inhibition of COX1, with decreased amounts of vasoactive prostaglandins, drives this inflammation to ulcers (Wallace et al., 2000). Interestingly small bowel damage occurs with long-term COX-2 absence or inhibition (small bowel inflammation and ulcers) although the mechanisms are unclear (Sigthorsson et al., 2002).
One of the more recent suggestions for reducing the intestinal side effects of NSAIDs is to attach a nitric oxide (NO) moiety to the NSAID, in the hope that the NO might counteract the effect of prostaglandin deficiency on the intestinal microcirculation. NO donors have been used in patients with cardiovascular disease for more than a century (Burgaud et al., 2002). NO is recognised as an important modulator of a large number of physiological processes (Wallace and Miller, 2000). More specifically, NO increases mucosal blood flow and mucus secretion and decreases leukocyte adherence (Cirino et al., 1996; Wallace and Miller, 2000). As these actions could, in theory, counteract the effects of mucosal prostaglandin deficiency induced by NSAIDs, a class of COX-inhibiting nitric oxide donors (CINODs) have been developed. CINODs are frequently produced by the addition of a nitroxybutyl moiety to the carboxylic group of the NSAID (which mediates the binding to the COX enzymes) by means of an ester linkage (Fiorucci, 2001). As well as potentially offering improved gastrointestinal tolerability, CINODs may result in enhanced anti-inflammatory, anti-pyretic and analgesic effects when compared to NSAIDs (Fiorucci et al., 2002) or COX-2 selective agents, although this is a controversial issue.
Previous animal studies have indicated that CINODs may offer reduced adverse gastrointestinal effects when compared to the parent compounds (Elliott et al., 1995; Davies et al., 1997). More recently, human studies have demonstrated that NO-aspirin (NCX-4016) maintains COX-1 and platelet inhibition whilst nearly avoiding the short-term gastric damage (Fiorucci, et al., 2003) and that AZD3582 [4-(nitroxy)butyl(2S)-2-(6-methoxy-2-naphthyl) propanoate] reduces gastrointestinal toxicity when compared to naproxen (Hawkey et al., 2003).
The precise reason that these CINODs reduce the gastrointestinal damage of the parent drug is controversial. Their ester linkage to the NSAID abolishes their topical effect and their effect on the COX enzymes. In order to maintain therapeutic efficacy the CINOD needs to undergo hydrolysis yielding the parent NSAID and the NO moiety. If the beneficial effects of CINODs are due to their counteracting or compensating for the vascular effects of prostaglandin deficiency it might be expected that CINODs would be equally associated with the permeability and inflammatory changes of the comparator NSAID (consequence of the topical effect) whilst reducing the number of ulcers. We tested this hypothesis by comparing the effects of AZD3582 with those of naproxen on small bowel permeability (using ${ }^{51} \mathrm{CrEDTA}$ ), intestinal inflammation (quantitated by measurement of granulocyte marker protein (GMP)) and small bowel ulcer counts in rats.
## Methods
## Animals
Male Sprague Dawley rats (Charles Rivers), 6-8 weeks old, weighing $200-250 \mathrm{~g}$ were used throughout these studies. Two groups of animals were used. The first group was used for the measurement of intestinal permeability and ulcer counts while the second group was used to assess intestinal inflammation via the measurement of granulocyte marker protein (GMP) in stool samples. Animals were housed singly in metabolism cages for up to 9 days and fed standard laboratory diet and water. For measurement of intestinal inflammation, stool samples were collected each day from day 2 to day 9 (with the drugs being administered on day 5). Following an overnight fast (day 4), animals received AZD3582 or naproxen diluted in solvent (oil in water emulsion) from $60 \mu \mathrm{mol} / \mathrm{ml}$ emulsions and given by gastric gavage at the doses of $10,30,100$ or $300 \mu \mathrm{mol} / \mathrm{kg}$ ( $\mathrm{n}=8$ in each group). Control animals received solvent only. Ulcer counts were performed 48 hours after administration of the drugs or vehicle. The naproxen and AZD3582 were obtained from AstraZeneca, R\&D Sodertalje, Sweden.
## Intestinal Permeability
One hour after administration of the study drugs or vehicle, the rats were administered $10 \mu \mathrm{Ci}{ }^{51} \mathrm{CrEDTA}$ via a tube in a volume of $0.5 \mathrm{ml}$ water followed by $1 \mathrm{ml}$ of water. Animals were allowed food and fluids 2 hours later. All urine passed during the following 5 hours was collected and the samples were assayed for gamma-radioactivity along with standards ( $10 \%$ of the dose given) in a Wallac 1284 gamma counter (Pharmacia, Sweden) for 1 minute. Results are expressed as percentage of the oral dose that was excreted in urine, which provides a measure of intestinal permeability as previously described (Somasundaram et al., 2000).
## Intestinal Inflammation
Stool samples were collected on each day of the study and $1 \mathrm{~g}$ wet weight of each were added to $4 \mathrm{ml}$ of extraction buffer (Tris $50 \mathrm{mM}$, $\mathrm{NaCl} 150 \mathrm{mM}, \mathrm{CaCl}_{2} 10 \mathrm{mM}$, Thiomersal $0.25 \mathrm{mM}, \mathrm{pH}$ to 8.4$)$. The samples were then homogenized for 30 seconds at $20,000 \mathrm{rpm}$ using an Ultra Turrax homogenizer (IKE Werke, Germany) and spun in a microcentrifuge for 10 minutes at $13,000 \mathrm{rpm}$. The supernatant was decanted off into an eppendorf tube and the samples were assayed for GMP as previously described (Sigthorsson et al., 2002). In short $50 \mu 1$ of a 1:200 dilution in duplicate to 96 well microtitre plates were added. The plates were pre-coated with anti-GMP antibody. Equal volumes of 9 standards were also added to the plates in duplicate. The plates were incubated at room temperature on a plate shaker for 45 minutes, washed 4 times with rinsing buffer (Tris $50 \mathrm{mM}, \mathrm{NaCl} 150 \mathrm{mM}, \mathrm{MgCl}_{2} 0.5 \mathrm{mM}, \mathrm{KCl}$ $2.5 \mathrm{mM}$, Thiomersal $0.25 \mathrm{mM}$, Tween- $200.05 \%, \mathrm{pH}$ to 8.0 ) allowed to dry and then $50 \mu \mathrm{l}$ of alkaline phosphatase (ALP) conjugated anti-GMP (diluted 1:800 in assay buffer) was added to each well. The plates were incubated under the same conditions as before, washed and dried as before and then $100 \mu \mathrm{l}$ of substrate (p-nitrophenyl phosphate, $1 \mathrm{mg} / \mathrm{ml}$, in substrate buffer ( $10 \%$ diethanolamine), $\mathrm{MgCl}_{2} 0.5 \mathrm{mM}$, Thiomersal $0.25 \mathrm{mM}, \mathrm{pH} 9.6$ ) was added to each well. The optical density of the highest standard was monitored and when it read between 1.2-1.8, the reaction was stopped by adding $50 \mu 11 \mathrm{M} \mathrm{NaOH}$ to each well. The plates were read at $405 \mathrm{~nm}$ using an MRX plate reader plus Dynex Revelation software (Dynex Technologies, USA). The results are expressed in $\mathrm{mg} / \mathrm{l}$ of extract.
## Macroscopic studies
To assess ulceration within the small bowel, animals were euthanazed by $\mathrm{CO}_{2}$ inhalation 48 hours after administration of the drugs. The abdomen was opened via a midline incision and the small intestine isolated, removed and gently flushed with $0.9 \%$ saline. The intestinal mucosa was exposed by cutting along the anti-mesenteric side of the intestine. Ulcer counts were performed by noting both the number and size of the ulcers ( $\leq 5 \mathrm{~mm}$ were recorded as pointed, $>5 \mathrm{~mm}$ were recorded as longitudinal).
## Statistical analysis
Results are presented as median and range as not all data was normally distributed. Wilcoxon's rank sum test was used to assess statistical differences between groups and the Wilcoxon's signed rank test for sequential data.
## Results
## Intestinal Permeability
Figure 1 shows that administration of both naproxen and AZD3582 significantly increased intestinal permeability at all doses given when compared with baseline (vehicle only) ( $p<0.001$ ). There was no significant difference ( $p>0.05$ ) in intestinal permeability between AZD3582 and naproxen at any of the doses given.
## Intestinal Inflammation
There was no significant increase in GMP with the 10 or $30 \mu \mathrm{mol} / \mathrm{kg}$ doses of either drug (Figure 2). Rats given AZD3582 at a dose of $100 \mu \mathrm{mol} / \mathrm{kg}$ had GMP values significantly higher than the control group ( $p<0.05$ ). At doses of $300 \mu \mathrm{mol} / \mathrm{kg}$, a significant increase in intestinal inflammation was noted with both naproxen and AZD3582 when compared to the vehicle group ( $\mathrm{p}<0.01$ ). No significant difference was observed between the two drugs at any of the dose range tested.
## Macroscopic examination
On macroscopic examination, no ulcers were seen with either drug over a dose range of $0-100 \mu \mathrm{mol} / \mathrm{kg}$. The mean number of ulcers with naproxen $300 \mu \mathrm{mol} / \mathrm{kg}$ ) was 17.1 (range 10 29). The rats treated with AZD3582 had significantly fewer ulcers ( $\mathrm{p}<0.001$ ) (median 2.5; range 0-12) (Figure 3).
Fig. 1 Urinary excretion of 51 CrEDTA after Naproxen and AZD3582. The white circles represent median (bars represent range) values obtained from rats dosed with naproxen. The black circles represent values obtained from rats dosed with AZD3582. Urinary excretion of $51 \mathrm{CrEDTA}$ was measured 5 hours following dosing.
Fig. 2 GMP concentrations after Naproxen and AZD3582. The white circles represent median (bars represent range) GMP values obtained from rats dosed with naproxen. The black circles represent the GMP values obtained from rats dosed with AZD3582. Data shown is taken from the day following dosing.
Fig. 3 Small bowel ulcer counts after Naproxen and AZD3582. The white circles represent the number of ulcers in rats dosed with naproxen. The black circles represent the number of ulcers in rats dosed with AZD3582. Counts were made 48 hours after dosing with $300 \mu \mathrm{mol} / \mathrm{kg}$.
## Discussion
These studies show that AZD3582 is associated with significantly less small bowel ulcerative damage than naproxen while the postulated consequences of the topical effect, intestinal permeability and inflammation, is equally evident with both drugs. The findings are consistent (assuming that the NO is released prior to or during drug absorption ren-dering intact naproxen) with the aforementioned pathogenic framework for NSAID-induced small bowel damage and the suggestion that the NO maintains vascular perfusion following the administration of naproxen.
A number of studies show that virtually all acidic NSAIDs increase small intestinal permeability, by virtue of their acidity and lipid solubility, and it is suggested that that this is a prerequisite for the development of small intestinal inflammation (Sigthorsson et al., 2000). Unlike non-selective NSAIDs, the NO moiety of AZD3582 renders the molecule non-acidic, and hence it can not exert a topical effect in this form. Nevertheless it is still associated with increased intestinal permeability in the current experiments suggesting hydrolyses of the ester bond, presumably by gastric and more importantly pancreatic esterases (Somasundaram et al., 1997). This raises the possibility that the beneficial action of AZD3582 on the stomach (Hawkey et al., 2003; WilderSmith et al., 2006) may simply be due to its lack of topical toxicity (Rainsford and Whitehouse, 1980).
While both drugs were associated with similar increases in intestinal permeability there were no inflammatory changes following the lower ( 10 or $30 \mu \mathrm{mol} / \mathrm{kg}$ ) doses of the drugs unlike previous studies where inflammation invariably follows the intestinal permeability changes (Somasundaram et al., 1997; Somasundaram et al., 2000). The reasons for this may be that much higher doses of NSAIDs were administered in previous studies. Indeed at the higher doses of 100 and $300 \mu \mathrm{mol} / \mathrm{kg}$, dose dependent inflammation was seen for naproxen and AZD3582, the inflammation being similar for both drugs. It is noteworthy that NO itself, despite its potentially beneficial effect on microvascular blood flow and healing, may be directly toxic to the epithelial cells at high concentrations (Menconi et al., 1998).
The results of studies on AZD3582 can not be extrapolated over to other NO-NSAIDs as their method of production, stability, pharmacokinetics and rate of hydrolyses may differ. A similar study to the current one (Davies et al., 1997) nevertheless found more contrasting degrees of inflammation with naproxen compared to the CINOD. This study used higher drug doses and a much stricter dosing regime (twice daily dosing for over 2 weeks compared to our single dose over 8 days). However, Somasundaram (1997) using nitroxybutyl-flurbiprtofen obtained almost identical results to the current study.
Previous studies have clearly dissociated the consequences of the topical effect (increased intestinal permeability and inflammation) from the COX-1 inhibitory effect, which seems to drive the inflamed mucosa to an ulcerated one (Somasundaram et al., 2000). The ulcerative damage with AZD3582 was significantly less than for naproxen. The precise mechanism for this is nevertheless uncertain. Estimates of the metabolism of CINODs and NO-releasing drugs suggest that the rate of NO release from these compounds both in vitro and in vivo is slow in comparison to other NO donors such as sodium nitroprusside (SNP) and S-nitroso-N-acetyl-D,L-penicillamine (Keeble and Moore, 2002). However NO certainly has the potential to increase microvascular blood flow (Whittle, 2003) and thus reduce the damage (Wallace et al., 2000), but it also increases mucous secretion, reduces secretion and adhesion of neu- trophils and reduces cytokine release from macrophages, all of which may be impaired by COX inhibition (Wallace et al., 2000). It has also been suggested that cytochrome P450 may play a role in the metabolism of CINODs (Grosser and Schroder, 2000). Alternatively the bioavailability of naproxen from a dose of AZD3582 may be lower than from a dose of naproxen.
In summary, AZD3582 is associated with equal changes in increased intestinal permeability and inflammation as equimolar doses of naproxen. At the same time it is associated with significantly less ulcerative small bowel damage. These findings are consistent to the suggestions that NO derived from AZD3582 counteracts the vascular effects of NSAID-induced inhibition of COX.
Acknowledgements. The drugs and solvents were supplied by AstraZeneca, Sweden who supported this project.
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