MOLPRINT MOLECULAR UNDERSTANDING OF PRINTABILITYJarl B. Rosenholm, bo Akademi University (coordinator)Martti Toivakka, bo Akademi UniversityKai-Erik Peiponen, University of JoensuuJussi Timonen, University of Jyvskyl (University of Oulu)Matti Murtomaa, University of TurkuHeidi Fagerholm, Top Analytica, Turku

NETWORK OF COMPETENCE IN FORMATION OF SURFACE PROPERTIES

MOLPRINT INDUSTRIAL PROJECT PARTNERSM-real OyjStoraEnso OyjOmya OyCiba Specialty (Raisio) Chemicals OyHansaprint OyKSV Instruments Oy

NETWORK OF COMPETENCE IN FORMATION OF SURFACE PROPERTIES

MOLPRINT New printing tech-niques require a range of coated and noncoated paper qualities.Advanced inks are pigment based, solvent based or water based, which should set fast without mottling

MOLPRINT WHY The diverging requirements set by new printing techniques has made the traditional specification standards used by paper manufacturers (Bendtsen, PPS, Cobb, HST) unsatisfactory, which is considered to be the greatest obstacle for a fast development of this industry. HOWPaper qualities aimed for different printing techniques are characterised thoroughly with physico-chemical and structural means in two- and three-dimensions, in order to establish new common standards for the printers and for the paper makers.

MOLPRINT Digital or Ink-Jet printingOffset or flexo printingBASE PAPER / SC / COATED PAPER / PACKAGES CALENDERING / SURFACE SIZING / COATING CALENDERING / SURFACE SIZING / COATING PRINTING METHOD A PRINTING METHOD B The research has to account for all the process stages

MOLPRINT WHAT will be done Chemical and physical surface and bulk properties Surface (2D) and cross-sectional (3D) structure 2D- and 3D- transport and setting of printing ink Optical properties related to visual response Heat transport and electric/hydrostatic conductivity

MOLPRINT WHOis doing

MOLPRINT

Pigment Coated PapersLaboratory of Paper Coating and Converting, bo Akademi UniversityTo understand the interactions that occur in various printing processes between printing liquids (inks, emulsified inks, foun-tain solutions) and pigment coated papers

Through use of both experiments and mathematical modeling, the project strives to identify those chemical and morphological properties of inks and coated paper surface that control the printability and quality of coated paper products

MOLPRINT

HOW it will be doneInfluence of ink constituents and paper surface characteristics on the ink tack development, ink setting and ink adhesion are investigatedInk constituents are separated chromatographicallyThe microstructure and chemistry in commercial inks is analyzed and consequences for the printability and print quality is evaluatedProperties ink/fountain solution emulsions are measured

MOLPRINT

EXPERIMENTAL PROCEDURESHg-porosimetryThin-layer wicking (TLW)Thin-layer chromatography (TLC, into latex)Tack, gloss, print density etc.RotogravureFlexoHeat/coldset offset

MOLPRINT

MODELING:Current models ignore chemistry!Develop 2D surface and 3D bulk model of coating structure, including heterogeneity caused by chemistryClarify the influence of nonuniformities on dominant mechanisms that control printability and print quality

MOLPRINT

Ink and Solvent Interaction and their Transport during PrintingDepartment of Physical Chemistry, bo Akademi University

Relate the surface energy and structure with the dynamic 2D-spreading and setting of inks on pigment coated papersInvestigate the simultaneous fast 2D- and 3D-penetration of model solutions into the bulk paper structure (ink-jet printing). A mathematical model is developed: which describes the liquid transport and ink setting processes serves as a new specification for printers and paper makers

MOLPRINT

HOW it will be doneThe surface energy and spreading is measured as wetting () The surface structure and interaction energy with AFM The setting speed, e.g. with D-QCMThe penetration is investigated as 2D-3D-liquid flow The amount of liquid absorbed is evaluated from volumetric and/or geometric considerationsThe binding of ink is characterized spectrometrically

MOLPRINT

Chart1

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mtn. 1

mtn. 2

mtn. 3

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tid [s]

q

HP-H2O-0,18 ml

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HP-papper kontaktvinkelmtning med jonbytt vattenpappretspapperets

2 varv med mikrometers skruv = ca. 0.2 mikroliter =0.1818mikrolitersvllningsvllning

0.469.350.049197861nlen=0.46mmunderca. 1.18mm

P vidobilden=9.35cmdroppenfrn droppens

medel punkt

[mm][mm][mm][mm][mm][mm]

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69911.50.4427820.4427820.8855640.56577795103.90591493630.2690664248-13.9059149363-0.24270400110.97069167640.456151021700

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159.259.2510.750.45508150.45508150.9101630.52887859098.57830665760.2495078061-8.5783066576-0.14971969540.98881292730.460230127900

209.259.510.50.45508150.4673810.92246250.51657982.596.47940059220.2447998451-6.4794005922-0.11308687390.99361249110.46419630800

309.59.5100.4673810.4673810.9347620.491988092.93760142880.231165025-2.9376014288-0.0512708170.99868593960.46799597500

409.59.759.750.4673810.47968050.94706150.479680577.590.73929012370.226744218-0.7392901237-0.01290304680.99991675680.473570171500

609.759.7590.47968050.47968050.9593610.44278272.585.41877991470.20548824914.58122008530.07995737420.99680511180.481217937500

909.751080.47968050.491980.97166050.3935846578.02370324840.177847427711.97629675160.20902581050.978233530.496640357400

1209.75106.750.47968050.491980.97166050.332086552.568.70867331010.142299034221.29132668990.37160375290.93174620510.52141908100

1809.75104.250.47968050.491980.97166050.20909153546.57212983640.082308456343.42787016360.75795932150.72624036770.668966187500

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5019.259.2512.250.45508150.45508150.9101630.6026755100105.88694362120.3106737911-15.8869436212-0.27727947430.96180371350.473154234700

10029.259.5120.45508150.4673810.92246250.59037697.5104.0025351150.3050232637-14.002535115-0.24439034140.97028502120.47535645700

49.59.5120.4673810.4673810.9347620.59037697.5103.26502923030.3103191718-13.2650292303-0.23151843540.97331910350.480192979200

69.759.5120.47968050.4673810.94706150.59037695102.53496280970.3156852244-12.5349628097-0.21877637260.97616375040.485093561200

10109.7511.750.491980.47968050.97166050.578076592.599.91089788010.3154730861-9.9108978801-0.17297779980.98507660680.493190323100

15101011.50.491980.491980.983960.56577787.597.98182619690.3099372741-7.9818261969-0.13930914750.99031216360.496792847800

201010.25110.491980.50427950.99625950.54117882.594.74368437960.2939219258-4.7436843796-0.08279291110.99657462430.499841896300

3010.2510.2510.50.50427950.50427951.0085590.5165798091.38055439570.278526187-1.3805543957-0.02409521970.99970972420.504425922600

4010.510.510.250.5165790.5165791.0331580.504279577.588.61944560430.27852521281.38055439570.02409521970.99970972420.516728993900

6010.510.59.750.5165790.5165791.0331580.47968057085.75780720670.2588594294.24219279330.07404023170.9972602740.517998173100

9010.7510.58.750.52887850.5165791.04545750.43048256578.94491969670.226538655711.05508030330.19294755040.9814432990.532612276800

12010.7510.57.50.52887850.5165791.04545750.36898557.570.43518593640.184677259219.56481406360.3414704230.94226327940.554758697900

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10029.59.5120.4673810.4673810.9347620.59037697.5103.26502923030.3103191718-13.2650292303-0.23151843540.97331910350.480192979200

49.759.5120.47968050.4673810.94706150.59037697.5102.53496280970.3156852244-12.5349628097-0.21877637260.97616375040.485093561200

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10101011.50.491980.491980.983960.56577792.597.98182619690.3099372741-7.9818261969-0.13930914750.99031216360.496792847800

1510.2510.2511.250.50427950.50427951.0085590.55347759095.32600153210.3098632327-5.3260015321-0.09295626270.99568267670.506466077800

2010.510.25110.5165790.50427951.02085850.5411788593.34967598110.304466979-3.3496759811-0.05846287470.99829153280.51130279400

3010.7510.510.250.52887850.5165791.04545750.50427958087.94169039140.28358803672.05830960860.03592427970.99935479250.523066236300

4010.7510.75100.52887850.52887851.0577570.4919877.585.85993869390.27851254784.14006130610.0722577010.9973905480.530262193800

601110.759.50.5411780.52887851.07005650.46738167.582.27853475020.26361512727.72146524980.13476499170.99093293370.539923774700

9010.7510.758.250.52887850.52887851.0577570.405883562.575.00828472050.213344430614.99171527950.26165479210.96596324030.547514106100

12010.7510.757.250.52887850.52887851.0577570.356685547.567.99291829650.180477845622.00708170350.38409603450.92713754650.570442327600

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5019.59.2512.50.4673810.45508150.92246250.61497595106.26020470830.3272800092-16.2602047083-0.28379410920.960.480449218800

10029.759.2512.250.47968050.45508150.9347620.602675595104.41211400280.3214146644-14.4121140028-0.25153884150.96853055920.482567117300

4109.512.250.491980.4673810.9593610.602675595102.96614738580.3324419609-12.9661473858-0.22630196320.97450280470.492231010200

6109.75120.491980.47968050.97166050.59037692.5101.09693258740.326627763-11.0969325874-0.19367801050.98130296950.495086904900

1010.251011.50.50427950.491980.99625950.5657779097.27637315570.3153486283-7.2763731557-0.12699666920.99194675540.502173879100

1510.2510.25110.50427950.50427951.0085590.5411788594.04272988070.2991623029-4.0427298807-0.07055894720.99751175010.505537403400

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3010.510.510.50.5165790.5165791.0331580.51657982.5900.28871467250010.51657900

4010.510.75100.5165790.52887851.04545750.491988086.52859082210.27351475383.47140917790.06058751980.99816513760.523689648400

6010.7510.759.50.52887850.52887851.0577570.46738172.582.93541083220.25881169177.06458916780.12330034130.99240813850.532924388200

9010.7510.7580.52887850.52887851.0577570.39358462.573.31221683190.204853051816.68778316810.29125676110.95788374520.552132242200

12010.7510.757.250.52887850.52887851.0577570.35668555567.99291829650.180477845622.00708170350.38409603450.92713754650.570442327600

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501101011.50.491980.491980.983960.56577792.597.98182619690.3099372741-7.9818261969-0.13930914750.99031216360.496792847800

1002101011.50.491980.491980.983960.5657779097.98182619690.3099372741-7.9818261969-0.13930914750.99031216360.496792847800

4101011.50.491980.491980.983960.5657779097.98182619690.3099372741-7.9818261969-0.13930914750.99031216360.496792847800

6101011.50.491980.491980.983960.56577787.597.98182619690.3099372741-7.9818261969-0.13930914750.99031216360.496792847800

101010.25110.491980.50427950.99625950.5411788594.74368437960.2939219258-4.7436843796-0.08279291110.99657462430.499841896300

1510.2510.2510.50.50427950.50427951.0085590.51657982.591.38055439570.278526187-1.3805543957-0.02409521970.99970972420.504425922600

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3010.510.59.750.5165790.5165791.0331580.47968057585.75780720670.2588594294.24219279330.07404023170.9972602740.517998173100

4010.510.759.50.5165790.52887851.04545750.46738172.583.60092058090.25406378746.39907941910.1116850050.993769710.526005919400

6010.7510.590.52887850.5165791.04545750.4427827080.53312333880.23550131779.46687666120.16522816760.98638085260.529946164900

9010.7510.57.50.52887850.5165791.04545750.3689856570.43518593640.184677259219.56481406360.3414704230.94226327940.554758697900

12010.7510.56.750.52887850.5165791.04545750.332086557.564.85510999150.161711518625.14489000850.43886112070.905236170.577450136600

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5019.259.25120.45508150.45508150.9101630.59037695104.74753272270.2997975001-14.7475327227-0.25739300260.96705690170.470583994800

10029.59.25120.4673810.45508150.92246250.59037695104.0025351150.3050232637-14.002535115-0.24439034140.97028502120.47535645700

49.59.5120.4673810.4673810.9347620.59037695103.26502923030.3103191718-13.2650292303-0.23151843540.97331910350.480192979200

69.59.75120.4673810.47968050.94706150.59037692.5102.53496280970.3156852244-12.5349628097-0.21877637260.97616375040.485093561200

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15101011.50.491980.491980.983960.5657779097.98182619690.3099372741-7.9818261969-0.13930914750.99031216360.496792847800

201010.2511.250.491980.50427950.99625950.553477587.596.02557500840.3045037562-6.0255750084-0.10516612320.99447513810.500897137500

301010.5110.491980.5165791.0085590.5411788594.04272988070.2991623029-4.0427298807-0.07055894720.99751175010.505537403400

4010.2510.510.50.50427950.5165791.02085850.51657977.590.6861687990.2835897416-0.686168799-0.01197590480.99992828970.510465855700

6010.2510.59.750.50427950.5165791.02085850.479680572.586.44239936870.25410056453.55760063130.06209184450.99807292070.511414786900

9010.2510.758.50.50427950.52887851.0331580.4181836577.9819880850.213582142512.0180119150.20975387750.97808219180.52815500

12010.510.57.250.5165790.5165791.0331580.35668555569.24831015990.173273423220.75168984010.36218531310.93512476010.552417198300

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250.59.259.25120.45508150.45508150.9101630.590376100104.74753272270.2997975001-14.7475327227-0.25739300260.96705690170.470583994800

5019.259.25120.45508150.45508150.9101630.590376100104.74753272270.2997975001-14.7475327227-0.25739300260.96705690170.470583994800

10029.59.25120.4673810.45508150.92246250.590376100104.0025351150.3050232637-14.002535115-0.24439034140.97028502120.47535645700

49.59.25120.4673810.45508150.92246250.59037697.5104.0025351150.3050232637-14.002535115-0.24439034140.97028502120.47535645700

69.59.5120.4673810.4673810.9347620.59037697.5103.26502923030.3103191718-13.2650292303-0.23151843540.97331910350.480192979200

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15101011.250.491980.491980.983960.55347759096.73292132690.2992100401-6.7329213269-0.11751164540.99310344830.495396527800

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3010.2510.2510.50.50427950.50427951.0085590.51657982.591.38055439570.278526187-1.3805543957-0.02409521970.99970972420.504425922600

4010.2510.2510.250.50427950.50427951.0085590.504279580900.26857931030010.504279500

6010.2510.259.50.50427950.50427951.0085590.4673817585.65051177080.24015326054.34948822920.07591289040.997120.505736019700

9010.2510.58.50.50427950.5165791.02085850.4181836078.65395572010.209433388811.34604427990.19802582980.98045687480.520603468800

12010.2510.57.250.50427950.5165791.02085850.35668555569.89132880.169734780420.10867120.35096252060.93904223150.543563678900

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3012.2513.2514.250.60267550.65187351.2545490.701071587.596.35966023970.6137291125-6.3596602397-0.11099701050.99384615380.6311585526000.4964912353-0.70018944863.401197381730

40131313.750.6395740.6395741.2791480.676472582.593.21200597860.5967492776-3.2120059786-0.05606007990.99842904520.6405803227000.4643660153-0.76708221163.688879454140

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412.251215.50.60267550.5903761.19305150.76256995103.93083698010.6584291684-13.9308369801-0.24313897290.97058704860.614603039300

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100211.751215.750.57807650.5903761.16845250.774868597.5105.96973243050.6590446375-15.9697324305-0.27872441160.96140717240.607678272800

411.751215.50.57807650.5903761.16845250.76256995105.08645258080.6410333378-15.0864525808-0.263308270.96553419940.605080845800

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412.2511.7515.50.60267550.57807651.1807520.76256992.5104.50638922550.6496859515-14.5063892255-0.25318425460.96811971370.609817145200

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3013.512.2514.250.6641730.60267551.26684850.701071582.595.80382093780.6222670107-5.8038209378-0.10129578460.99487396740.636687933100

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901512.75120.737970.62727451.36524450.5903767081.71075251780.53986697698.28924748220.14467466110.98955286250.689828988300

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1002121215.750.5903760.5903761.1807520.774868597.5105.3921034440.6678368094-15.392103444-0.26864288390.96413199430.612339392900

4121215.50.5903760.5903761.1807520.76256995104.50638922550.6496859515-14.5063892255-0.25318425460.96811971370.609817145200

61212.2515.50.5903760.60267551.19305150.76256995103.93083698010.6584291684-13.9308369801-0.24313897290.97058704860.614603039300

1012.2512.515.250.60267550.6149751.21765050.750269592.5101.88303958750.6579715244-11.8830395875-0.20739816590.97856998180.622158109600

1512.512.7514.750.6149750.62727451.24224950.72567059098.87743273540.6398474577-8.8774327354-0.15494043040.98802072540.628655587900

201312.7514.50.6395740.62727451.26684850.7133719096.79426583870.6396820824-6.7942658387-0.11858230910.9929773530.637904024800

3013.2513.2513.750.65187350.65187351.3037470.67647258592.12182338050.6136277927-2.1218233805-0.03703280410.99931436410.652320754500

4013.7513.513.250.67647250.6641731.34064550.651873577.588.40115177340.60513909311.59884822660.02790516580.99961067610.670583824300

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100211.2511.515.750.55347750.5657771.11925450.774868597.5108.32469409140.624796596-18.3246940914-0.31982624630.94929006090.589521868100

411.511.515.50.5657770.5657771.1315540.76256997.5106.8539380430.6156191165-16.853938043-0.29415671080.95704697990.591169516100

611.511.7515.50.5657770.57807651.14385350.76256997.5106.26020470830.6239999203-16.2602047083-0.28379410920.960.595757031200

1011.51215.250.5657770.5903761.1561530.750269595104.77208630250.6149605378-14.7720863025-0.25782154340.96694772340.597836352500

151212150.5903760.5903761.1807520.7379795102.68038349180.6144656295-12.6803834918-0.22131444230.97560975610.605135400

201212.2514.750.5903760.60267551.19305150.725670592.5101.15727251080.6057046329-11.1572725108-0.19473114090.981099730.608017443900

3012.2512.514.250.60267550.6149751.21765050.701071587.598.0565273330.5886151973-8.056527333-0.14061292820.99013028030.614894082200

4012.751313.750.62727450.6395741.26684850.676472597.593.7645648860.5884305809-3.764564886-0.06570405220.99784226520.63479396700

601313.25130.6395740.65187351.29144750.6395748089.45171921250.55587842830.54828078750.0095693050.99995421460.645753316100

9013.2513.5120.65187350.6641731.31604650.5903767083.79667194030.50928398446.20332805970.10826849920.99414468910.661898873700

12013.2513.7511.250.65187350.67647251.3283460.55347756579.61114218450.472291540210.38885781550.18131977440.98360655740.6752425500

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10.0210120.491980.5903761.082356000901.57079632680883448855249733000

50.111.2512.250.55347750.60267551.156153000901.57079632680943684004471306000

70.1411.512.250.5657770.60267551.1684525000901.57079632680953723196008235000

100.211.512.50.5657770.6149751.180752000901.57079632680963762387545164000

150.311.512.50.5657770.6149751.180752000901.57079632680963762387545164000

200.411.512.50.5657770.6149751.180752000901.57079632680963762387545164000

250.51314.58.250.6395740.7133711.3529450.400963747.561.31275737910.321973848328.68724262090.50068683710.87725306770.77112583010.10.00491980

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350.71415.57.50.6887720.7625691.4513410.35422564552.0373004520.31627976937.9626995480.66257410010.78841139190.92042112470.30.01475940

400.814.5167.250.7133710.7871681.5005390.337006342.548.3773564880.318024371341.6226435120.72645217270.74753564591.00365715550.40.01967920

450.914.51670.7133710.7871681.5005390.31978742.546.17026734560.299881283843.82973265440.76497314510.72140095521.04001733650.50.0245990

50115166.50.737970.7871681.5251380.29026824041.67816975340.277946965148.32183024660.84337503840.664945831.14681371860.60.02951880

601.215166.50.737970.7871681.5251380.285348441.03104974620.272812888148.96895025380.85466941320.65646792511.16162415690.70.03443860

701.4151660.737970.7871681.5251380.255829632.537.09154448550.24245099152.90845551450.92342675090.60309027651.26443590580.80.03935840

801.6151660.737970.7871681.5251380.250909836.42574654050.23746094453.57425345950.93504711720.59378051531.28426073330.90.04427820

901.815165.750.737970.7871681.5251380.233690534.07553559130.220143573955.92446440870.97606603630.56028537461.361036776310.0491980

100215165.750.737970.7871681.5251380.2213913032.37841251410.207908233657.62158748591.00568642190.53550863721.42400877781.250.061497510.049198

1202.415165.250.737970.7871681.5251380.1967923028.94058820010.183747357761.05941179991.06568777520.4839024391.57587343751.250.061497510.049198

1402.8151650.737970.7871681.5251380.159893527.523.68415223070.148192875366.31584776931.15742988980.40169449291.89838051921.750.08609651.250.0614975

1603.2151650.737970.7871681.5251380.14759421.90812528680.136501154768.09187471321.18842740760.37311935812.043766916720.0983961.50.073797

1803.6151650.737970.7871681.5251380.14759421.90812528680.136501154768.09187471321.18842740760.37311935812.043766916720.0983961.50.073797

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5151650.737970.7871681.5251380.09839614.70475871980.090377263375.29524128021.31414987140.25383828053.00415287530.1475942.50.122995

615164.750.737970.7871681.5251380.086096512.88320019870.078977811477.11679980131.34594206510.22296429493.420139535730.1475942.50.122995

715164.750.737970.7871681.5251380.06149759.22129863730.056295814980.77870136271.40985430430.16024812614.758676553.50.17219330.147594

815164.750.737970.7871681.5251380.03689855.54043159440.03373072684.45956840561.47409755350.09654814437.898328916740.1967923.250.1598935

10151650.737970.7871681.5251380.0245993.6952205320.022477408486.3047794681.50630256190.064449064411.8321194.50.22139140.196792

1515165.750.737970.7871681.5251380.01229951.84809070550.011235781588.15190929451.53854105910.032249674923.645788755.50.2705894.750.2336905

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20.0412.25120.60267550.5903761.1930515000901.57079632680973801579082093000

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100.212.5120.6149750.5903761.205351000901.57079632680983840770619021000

120.2413.7514.2570.67647250.70107151.3775440.341926152.80223040470.275733415837.19776959530.64922355380.79655345320.86469024420.050.00245990

150.31414.56.50.6887720.7133711.4021430.314867248.37187159130.259437551941.62812840870.72654790220.74747205690.93792335590.10.00491980

200.414.5156.250.7133710.737971.4513410.300107844.93599394490.262394889945.06400605510.78651527980.70631641961.02740143070.150.00737970

250.514.51560.7133710.737971.4513410.285348442.93152284990.248199190747.06847715010.82149990020.68112379451.06540177540.20.00983960

300.614.51560.7133710.737971.4513410.282888542.59470809810.245852499447.40529190190.82737842660.676807981.07219554350.250.01229950

350.714.5155.750.7133710.737971.4513410.268129140.55768826410.231883647449.44231173590.86293112960.65021333391.11604985960.30.01475940

400.814.5155.750.7133710.737971.4513410.258289539.18456378210.222673646250.81543621790.88689667280.63182049971.14853902380.50.0245990

450.914.5155.50.7133710.737971.4513410.2459937.45157569050.211271271652.54842430950.91714302090.60809069831.19335898750.50.0245990

50114.5155.50.7133710.737971.4513410.2459937.45157569050.211271271652.54842430950.91714302090.60809069831.19335898750.50.0245990

601.214.5155.50.7133710.737971.4513410.2459937.45157569050.211271271652.54842430950.91714302090.60809069831.19335898750.50.0245990

701.414.5155.250.7133710.737971.4513410.233690535.70063660440.199985804454.29936339560.9477026730.58355023431.24354418420.50.0245990.10.0049198

801.614.51550.7133710.737971.4513410.22139133.93229621710.188811399456.06770378290.9785660350.55821287781.29998881940.50.0245990.20.0098396

901.814.51550.7133710.737971.4513410.22139133.93229621710.188811399456.06770378290.9785660350.55821287781.29998881940.50.0245990.30.0147594

100214.51550.7133710.737971.4513410.22139133.93229621710.188811399456.06770378290.9785660350.55821287781.29998881940.50.0245990.40.0196792

1202.414.51550.7133710.737971.4513410.19679230.34583069110.16677239459.65416930891.0411616670.50521808941.436350984410.0491980.50.024599

1402.814.51550.7133710.737971.4513410.19679230.34583069110.16677239459.65416930891.0411616670.50521808941.436350984410.0491980.750.0368985

1603.214.5154.750.7133710.737971.4513410.159893524.85188573090.134400717365.14811426911.13704909550.42027397261.72666057691.50.07379710.049198

1803.614.5154.750.7133710.737971.4513410.159893524.85188573090.134400717365.14811426911.13704909550.42027397261.72666057691.50.07379710.049198

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514.5154.250.7133710.737971.4513410.110695517.34634809580.092275061172.65365190421.26804543930.29814710842.433934388920.0983961.50.073797

614.5153.750.7133710.737971.4513410.07379711.61345381110.061253665678.38654618891.36810332030.20130793293.60477845832.250.11069551.750.0860965

714.5153.50.7133710.737971.4513410.0491987.75704900570.040757838882.24295099431.43541028140.13497283395.37641893752.50.12299520.098396

814.5153.50.7133710.737971.4513410.0245993.88297278180.020355537986.11702721821.5030256670.067718794810.71593937530.1475942.50.122995

1014.5153.50.7133710.737971.4513410.01229951.94204386220.010174846388.05795613781.53690126720.033888569821.41342953.250.159893530.147594

1514.5154.50.7133710.737971.4513410.01229951.94204386220.010174846388.05795613781.53690126720.033888569821.41342954.250.20909153.750.1844925

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3014.5155.250.7133710.737971.4513410.01229951.94204386220.010174846388.05795613781.53690126720.033888569821.413429550.245994.50.221391

4014.5155.50.7133710.737971.4513410.0245993.88297278180.020355537986.11702721821.5030256670.067718794810.71593937550.245994.50.221391

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160.32141470.6887720.6887721.3775440.3443865053.13010235420.278021536536.86989764580.64350110880.80.86096500

200.41514.56.750.737970.7133711.4513410.33208654549.18023433240.293870291740.81976566760.71243931080.75676959620.95890546300

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300.615.2514.7560.75026950.72567051.475940.29518837.543.60281897270.265987861646.39718102730.80978357260.68965517241.070056500

400.815.25155.750.75026950.737971.48823950.282888541.63013193270.257902005548.36986806730.84421345650.66431938891.120123486400

50115.25155.50.75026950.737971.48823950.265669239.2956490.240889676250.7043510.884957870.63332210591.17494674990.10.00491980

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1402.815.25154.750.75026950.737971.48823950.20909152531.38984828680.186648367758.61015171321.02294012250.52085839081.42864118750.50.0245990.10.0049198

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300.614.514.560.7133710.7133711.4267420.2951883544.95886879420.249433764745.04113120580.78611603840.70659898481.009583958300

350.714.7514.560.72567050.7133711.43904150.29518844.61241010980.253519680545.38758989020.79216288310.70230725941.024509914100

400.814.7514.55.750.72567050.7133711.43904150.282888542.92577184940.241903219147.07422815060.82160027410.68105030051.056486942900

450.914.7514.55.750.72567050.7133711.43904150.282888542.92577184940.241903219147.07422815060.82160027410.68105030051.056486942900

50114.7514.55.750.72567050.7133711.43904150.282888532.542.92577184940.241903219147.07422815060.82160027410.68105030051.056486942900

601.214.7514.55.50.72567050.7133711.43904150.265669240.53139494190.22586472949.46860505810.86339003460.64986461151.10718561560.10.00491980

701.414.7514.55.50.72567050.7133711.43904150.26074943039.8403401750.221328458350.1596598250.87545121560.64065046531.12310969710.20.00983960

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901.814.7514.55.250.72567050.7133711.43904150.23861032536.6935126250.201155204553.3064873750.93037371740.59753436131.20414957980.40.01967920

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1803.614.7514.54.750.72567050.7133711.43904150.20909151532.40754842980.174823177857.59245157021.00517790420.53593802631.34254468750.50.0245990

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714.7514.540.72567050.7133711.43904150.135294521.29843931850.111320504868.70156068151.19906843520.3632258521.98091833521.250.06149750

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1014.7514.53.250.72567050.7133711.43904150.07379711.71202717090.060223418678.28797282911.36638289060.20299284323.54456215621.750.086096510.049198

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3014.7514.53.750.72567050.7133711.43904150.01229951.95863930870.010003138488.04136069131.5366116220.034178047221.05213168753.50.17219330.147594

4014.7514.540.72567050.7133711.43904150.01229951.95863930870.010003138488.04136069131.5366116220.034178047221.05213168753.750.184492530.147594

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6014.7514.51.50.72567050.7133711.43904150.0245993.91613485850.020012122286.08386514151.50244687960.068296242210.535290468810.0491980.50.024599

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100.211.5120.5657770.5903761.156153000901.57079632680943684004471306000

140.2813.2513.57.250.65187350.6641731.31604650.356685556.92035199750.266358799233.07964800250.5773487730.83791264430.78531247200

150.313.2513.7570.65187350.67647251.3283460.34438654.81515087560.260017787135.18484912440.6140914640.81729729730.812645535700

200.413.7514.256.50.67647250.70107151.3775440.31978749.80953761620.255427220740.19046238380.70145589650.76390346270.901647961500

250.51414.56.250.6887720.7133711.4021430.307487547.36417544910.252617544642.63582455090.74413551770.73567372230.9529652600

300.614.2514.560.70107150.7133711.41444250.29518845.31046541740.245382921144.68953458260.77997951970.71092794130.994786122400

400.814.2514.55.50.70107150.7133711.41444250.265669241.17759627750.218541645448.82240372250.85211169370.65839520151.07415918040.10.00491980

50114.2514.55.50.70107150.7133711.41444250.260749440.47742251860.214140987449.52257748140.86433203110.64914835891.08946012160.20.00983960

601.214.2514.55.250.70107150.7133711.41444250.243530138.00207069660.198892370951.99792930340.90753507060.6156899541.14866459230.30.01475940

801.614.2514.550.70107150.7133711.41444250.226310835.48934325010.183870601654.51065674990.95139043770.58055152391.21818860310.40.01967920

100214.2514.550.70107150.7133711.41444250.22139134.76477776250.179618088755.23522223750.96403649110.57020866331.24028499650.50.0245990

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1402.814.2514.54.50.70107150.7133711.41444250.184492529.24174797730.148235010760.75825202271.06043154560.48849557521.44775364580.750.03689850

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150.3141470.6887720.6887721.3775440.3443864553.13010235420.278021536536.86989764580.64350110880.80.86096500

200.414.514.56.50.7133710.7133711.4267420.3197874048.29108392080.272752906841.70891607920.7279579130.74653465350.955576538500

250.514.514.7560.7133710.72567051.43904150.29518837.544.61241010980.253519680545.38758989020.79216288310.70230725941.024509914100

370.7414.5155.750.7133710.737971.4513410.27796873541.91876093080.241175203248.08123906920.83917593020.6680762371.08620911770.10.00491980

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751.514.5155.50.7133710.737971.4513410.258289532.539.18456378210.222673646250.81543621790.88689667280.63182049971.14853902380.250.01229950

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150314.51550.7133710.737971.4513410.1967923030.34583069110.16677239459.65416930891.0411616670.50521808941.436350984410.0491980.50.024599

414.5154.750.7133710.737971.4513410.1475943022.99312603520.123769931967.00687396481.16949057220.39062068971.85773697921.750.08609651.50.073797

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200.419.5207.50.9593610.983961.9433210.36898537.541.5882299110.573518790448.4117700890.84494478480.66377258091.4638454917000

250.519.75207.50.97166050.983961.95562050.36898537.541.34884952170.580467477748.65115047830.84912276070.66064194451.4800910812000

370.7419.75207.250.97166050.983961.95562050.35668553540.08190362440.559451656249.91809637560.87123513810.64388200381.5186171444000

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62020.57.250.983961.0085591.9925190.23369052526.40217435140.371021423963.59782564861.10999145470.44466917082.24045102632.50.1229952.50.122995

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30.0618189.250.8855640.8855641.7711280.45508155054.3962558970.609942284935.6037441030.62140256060.81306271941.089170587800

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150.318.518.58.50.9101630.9101631.8203260.4181834549.35372634070.582448572140.64627365930.7094113040.75874547651.19956300

200.418.518.58.50.9101630.9101631.8203260.40588354548.06857631890.563163711841.93142368110.73184140330.74394516371.22342753790.250.01229950

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901918.58.750.9347620.9101631.8449250.430482550.03378695620.617173985839.96621304380.69754200720.76642335771.203593928600

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150.318.518.758.50.9101630.92246251.83262550.41818342.549.0616207350.589826894440.9383792650.71450950860.75541472511.212992968800

200.418.518.758.50.9101630.92246251.83262550.4181834049.0616207350.589826894440.9383792650.71450950860.75541472511.212992968800

250.518.518.758.250.9101630.92246251.83262550.405883537.547.78218480310.570325024642.21781519690.73683987820.74059569981.237264475400

370.7418.518.7580.9101630.92246251.83262550.39358437.546.48996769450.55101605243.51003230550.75939332140.72525383121.263437310500

50118.518.7580.9101630.92246251.83262550.381284537.545.18511047270.531894131444.81488952730.78216737620.70938759841.29169547380.250.01229950

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150318.51980.9101630.9347621.8449250.31978737.538.23945265990.444565960951.76054734010.90339197370.61894937311.49036825961.50.0737970

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518.5198.250.9101630.9347621.8449250.28288853034.09806194420.389976020755.90193805580.97567287730.56061098471.64545919572.50.1229952.50.122995

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4018.5198.750.9101630.9347621.8449250.01229951.52779692190.016441086388.47220307811.54413124020.026661926834.59849358.50.41818380.393584

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200.417.519.57.750.8609650.9593611.8203260.381284542.545.45946415990.525166837644.54053584010.7773790010.71275438871.276965830600

250.517.519.57.50.8609650.9593611.8203260.3689854044.13579912480.50644313345.86420087520.80048131410.69636135511.307026866700

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5011819.570.8855640.9593611.8449250.34438637.540.94455903950.481709410649.05544096050.85617896080.65532844441.407633848200

751.518.2519.56.750.89786350.9593611.85722450.33208653539.35571504240.468996941750.64428495760.88390951980.63413306371.464380747700

100218.2519.56.50.89786350.9593611.85722450.31978732.538.00443046560.450284197251.99556953440.90749388480.61572240741.508167055300

150318.2519.56.50.89786350.9593611.85722450.30748753036.64208172530.431723432553.35791827470.93127135590.59681435521.55594824750.250.01229950

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1018.2519.56.50.89786350.9593611.85722450.1967922523.93025767550.270551149666.06974232451.15313453950.40562434422.28934052732.50.1229950

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100219.2519.570.94706150.9593611.90642250.3197873037.09154448550.473537091852.90845551450.92342675090.60309027651.58054488220.50.0245990

150319.2519.570.94706150.9593611.90642250.30748753035.75739319170.454081984954.24260680830.94671208370.58435438271.63122118750.750.03689850

200419.2519.570.94706150.9593611.90642250.2951883034.41314517610.434773012455.58685482390.97017363750.56515629151.686632997410.0491980

519.2519.570.94706150.9593611.90642250.28288853033.05905948730.415604328856.94094051270.99380689110.54550323251.74739798641.250.06149750

619.2519.56.750.94706150.9593611.90642250.258289527.530.32248515630.37766444759.67751484371.04156912340.50486641591.88804646131.50.0737970

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150.320.518.257.751.0085590.89786351.90642250.38128453543.60281897270.573209229146.39718102730.80978357260.68965517241.382156312500

210.4220.518.57.51.0085590.9101631.9187220.3689853542.07502205080.559752936547.92497794920.83644865920.67010309281.431661800

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881.7620.519.2571.0085590.94706151.95562050.3197873036.22004699980.497397905153.77995300020.93863725140.59088797571.65481493990.50.0245990

100220.519.2571.0085590.94706151.95562050.3197873036.22004699980.497397905153.77995300020.93863725140.59088797571.65481493990.50.0245990

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720.519.256.751.0085590.94706151.95562050.23369052526.88240967420.357652324863.11759032581.10160976710.4521608982.162527220420.0983960

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200.422.5219.751.1069551.0331582.1401130.479680542.548.29108392080.920541060441.70891607920.7279579130.74653465351.433364807700

250.52321.59.251.1315541.0577572.1893110.45508154045.14827615730.905919833644.85172384270.78281025630.7089343381.544085878400

310.622321.591.1315541.0577572.1893110.44278237.544.04611099360.878875240345.95388900640.80204666730.6952370621.574506826400

400.823.2521.591.14385351.0577572.20161050.4427823543.82339917960.888265832446.17660082040.80593372170.69243787781.589753081600

50123.521.58.751.1561531.0577572.213910.43048253542.50101101430.87035171247.49898898570.82901374920.67560321721.638469107100

681.3623.2521.58.51.14385351.0577572.20161050.4181833541.60239362880.834280401248.39760637120.84469758130.66395745261.657945468800

861.7223.521.58.51.1561531.0577572.213910.405883532.540.27260685650.816244989349.72739314350.86790673880.64642507351.71242584090.250.01229950.250.0122995

100223.2521.58.51.14385351.0577572.20161050.405883532.540.47938273920.807588722349.52061726080.86429781880.64917438251.69570038450.250.01229950.250.0122995

1262.5223.521.58.51.1561531.0577572.213910.3935843039.14625166080.789483896650.85374833920.88756534550.63130206051.75344746880.50.0245990.50.024599

150323.2521.58.51.14385351.0577572.20161050.381284532.538.20897010180.754778211151.79102989820.90392399470.61853141981.77970789310.750.03689850.750.0368985

200423.521.58.251.1561531.0577572.213910.35668553035.72018814140.710299548754.27981185860.94736143430.58382731241.896031543110.04919810.049198

523.2521.58.251.14385351.0577572.20161050.3443863034.74449696820.676906880255.25550303180.96439045780.5699178441.93151567631.250.06149751.250.0614975

623.521.58.51.1561531.0577572.213910.332086527.533.3984884680.658367304956.6015115320.98788273780.55045871562.010968251.750.08609651.750.0860965

823.2521.58.51.14385351.0577572.20161050.3197873032.39745714730.625820754157.60254285271.00535403030.53578932222.054548689920.09839620.098396

1023.521.58.51.1561531.0577572.213910.30748752531.04822199350.607066361358.95177800651.02890262610.51575931232.146262752.250.11069552.250.1106955

1523.2521.58.51.14385351.0577572.20161050.27058922.527.62015418380.525425