Estimated Ultimate Recovery (EUR) as a Function of Production Practices in the Haynesville Shale

合集下载

外贸专用词汇西班牙语

外贸专用词汇西班牙语

外贸常用词汇Ι.T é RMINOS GENERALES总类Comercio internalcional 国际贸易Importaci ó进n口Exportaci ó出n口Comercio visible 有形贸易Comercio invisible 无形贸易Comercio directo 直接贸易Comercio indirecto 间接贸易Puerto franco 自由港Divisas 外汇Tasa de cambio 汇率Fluctuaci ó浮n动Inflaci ó通n货膨胀Revaluació升n值Devaluació贬n值Aduana xxArancel 关税Tarifa 税率Barreras aduaneras/arancelarias 关税壁垒 Control de exportaci出口ón管束Arancel antidumping 反畅销税Arancel ad valorem 从价税1 / 5Subsidio de exportaci出口ó补n贴Dumping畅销Cuota de importaci进ó口n配额Permiso de importaci 进ó口n允许证 Cá mara internacional de Comercio国际商会ΙΙ .PROCESO DE UNA TRANSACCI交óN易程序Negociació洽n谈Comfirmació确n认Oferta/Cotizaci报ó盘n/ 报价Lista de precios 价目表Cat á logo商品目录 Pedido 订货Orden 定货Pr á ctica老例Sujeto(a) a nuestra confirmaci需ó经n我final方最后确认Ⅲ.CALIDAD,CANTIDAD,EMBALAJE Y ETIQUETA质量,数目,包装和商标Calidad 质量 Sistema americano 美制Muestra 样品 Pieza/Unidad 件Muestra original 原样 Caja 箱Descripci ó说n明 Embalaje exterior 外包装Folleto 宣传小册 Embalaje interior 内包装Art culoí N /Referencia°货号集装箱 Peso bruto 毛重 Cart ó纸n箱Tara 皮重 Rellenos 衬垫物2 / 5Volumen 体积 Embalaje usual/convencional 习惯包装 Sistema m é trico公制Marca 麦头Sistema ingl英é制s Marca registrada注册商标Ⅳ.PRECIOS价钱Precio al por menor 零售价Existencias/ Stock Producto disponible 现货 Precio unitario 单价Precio al por mayor 批发价FOB(Franco a bordo)·(puerto· de carga) ··港离岸价CIF(Costo,seguro y flete)...(puerto final)港成本、保险加运费到岸价Barca/vapor/buque 轮船Flete 运费Fletamento de un buque 租船Puerto de carga 货运港Puerto de descarga卸货港Seguro 保险Pó liza保单,保险单 C&F (Costo y flete)......港成本家运费到岸价Ex F á brica 工厂交货价Comisi ó佣n金Descuento 折扣3 / 5Ⅴ.EMBARQUE装运Puerto de destino 目的港Entrega/servicio 交货Plazo de entrega 交货限期Espacio 舱位Conocimientos 提单Ⅵ .SEGURO保险Prima 保费,保险费Ⅶ .PAGO支付Carta de cré dito irrevocable confirmada不行取消的保兑信誉证A nuestro/su favor 以.我方 / 贵方为仰头 Abrir una carta de cr开é信dito用证Factura 发票Factura proforma 形式发票Certificado de origen 原产地证明 Factura consular 领事发票Letra de cambio 汇票Cheque 支票A......d as vistaí见票后 ......天付款T/T(Transferencia telegr电汇á fica)D/A (Documento contra aceptaci 承兑ó交n)单 D/P(Documento contra pago)付款交单Carta de cré dito(L/C)信誉证4 / 5Ⅷ.INSPECCIN DEó MERCANCASí商品查验Certificado de inspecció n de质calidad量查验Inspecció n y aceptaci查收ó n证书Ⅸ .DISCREPANCIA Y ARBITRAJE争议与仲裁Reclamaci ó索n赔 Fuerza mayor 不行抗力,人力不行抗拒Disputa 争议Ⅺ.FORMAS DE COMERCIO贸易方式Trueque 易货贸易Representante 代理Representante exclusivo 独家代理Embalaje neutral 中性包装Concurso 招标 Comprador 来样加工Montaje final 组装Montaje de material fabricado en otro pa s 来件组 Licitacií拍ó卖n装Elaboraci ó n seg ú n la muestra provista por elⅫ .COMERCIO TECNOLGICOó技术贸易Propiedad industrial 工业产权Proyecto “ llave en mano交钥匙””工“程Know-How 专有技术 / 技术窍门Patente 专利5 / 5。

石油单词

石油单词

1.petroleum 石油,crude oil 原油,natural gas 天然气,seep 油气苗,tar 沥青,asphalt 沥青,bitumen 沥青,oil shale 油页岩,exploration 勘探,drilling 钻井,completion完井,production生产、采油,trap 圈闭,fault 断层,migration 运移,impermeable 非渗透性,reservoir 油气藏,gas cap 气顶,drilling rig,rig 钻机,drilling bit,bit钻头,drilling mud,mud 泥浆,casing 套管,run 下入,porosity 孔隙度,pore pressure 空隙压力,well logging,log 测井,string 管柱,perforation 射孔,perforating gun 射孔枪,tubing 油管,refining 炼化,2. petroleum geology 石油地质geology 地质学,atmosphere 大气圈,hydrosphere 水圈,ithosphere 岩石圈,exploration 勘探,hydrocarbon 烃,oil and gas generation 油气生成,oil and gas migration 油气运移,oil and gas accumulation 油气聚集,reservoir 油藏,oil and gas segregation 油气分离,core 地核,mantle 地幔,crust 地核,consolidated 固结的,unconsolidated 未固结的,igneous rock 火成岩,sedimentary rock 沉积岩,metamorphic rock 变质岩,magma 岩浆,mineralogy 矿物学,metamorphism 变质作用,sediment 沉积物,clastic sedimentary rock 碎屑沉积岩,chemical sedimentary rock 化学沉积岩,biogenic sedimentary rock 生物沉积岩,diagenesis 成岩作用,compaction 压实作用,cementation 胶结作用,recrystalization 重结晶作用,authigenesis 自生作用,shale 页岩,conglomerate 砾岩,sandstone 砂岩,siltstone 粉砂岩,limestone 石灰岩,dolostone 白云岩,kerogen 干酪根,dry gas 干气,wet gas 湿气,methane 甲烷,ethane 乙烷,propane 丙烷,butane 丁烷,primary petroleum migration 初次运移,secondary petroleum migration 二次运移,trap 圈闭,petroleum trap 油气圈闭,structural trap 构造圈闭,stratigraphic trap 地层圈闭,depositional trap(lithologic trap),anticlinal trap 背斜圈闭,oil/water contact 油水界面,gas cap 气顶,fault trap 断层圈闭,granite 花岗岩,normal fault 正断层,thrust fault 逆断层,anticline 背斜,pinchout间灭,unconformity 不整合,source rock 烃源岩,oil source bed 生油层,oil reservoir bed 储集层,cap rock,seal rock 盖层,petroleum reservoir 油气藏,petroleum field 油气田,petroleum zone 油气聚集带,petroleum generative basin 含油气盆地,LNG(liquefied natural gas)液化天然气,LPG(liquefied petroleum gas)液化石油气,calcite 方解石,seismic reflection 地震反射3. petrophysics 油层物理,reservoir fluid 储层流体,reservoir rock 储层岩石,interstitial water(connate water)间隙水(原生水),irreducible water 束缚水,aquifer 水体,dissolved gas 溶解气,saturated reservoir 饱和油藏,unsaturated reservoir 未饱和油藏,crude oil 原油,API degree API重度,API(American Petroleum Institute)美国石油学会,SG(specific gravity)比重,℃(centigrade)摄氏度,℉(fahrenheit)华氏度,condensate gas凝析气,volatile oil 挥发油,black oil 黑油,heavy oil 重油,paraffin 烷烃,naphthene 环烷烃,aromatic 芳香烃,oxygen compound 氧化物,sulfur compound 硫化物,nitrogen compound 氮化物,phase 相,phase behavior 相态,formation volume factor(FVF)地层体积系数,density 密度,viscosity 粘度,shear rate 剪切速率,shear stress 剪切应力,compressibility 压缩性,compressibility coefficient 压缩系数,pore 孔隙,primary pore 原生孔隙,fracture pore 裂缝孔隙,vuggy pore 孔洞孔隙,secondary pore 次生孔隙,porosity 孔隙度,tight gas 致密气,shale gas 页岩气,saturation 饱和度,irreducible water saturation 束缚水饱和度,residual oil saturation 残余油饱和度,permeability 渗透率,Darcy 达西,millidarcy(md)毫达西,Darcy's law 达西定律,Darcy flow 达西流,non-Darcy flow 非达西流,absolute permeability 绝对渗透率,relative permeability 相对渗透率,multiphase flow 多相流,porous media 多孔介质,effective permeability 有效渗透率,EUR(estimated ultimate recovery)最终采收率,water cut 含水率,wettability 润湿性,water-wet水湿,oil-wet 油湿,neutral wet 中性润湿,mixed wet 混合润湿,preferential wettability 选择性润湿,contact angle 接触角,carbonate formation 碳酸盐岩储层,capillary pressure 毛细管力,reservoir heterogeneity 储层非均质性,homogeneous 均质的,preferential flow channel 优势通道,lateral similarity 平面相似,vertical variation 垂向变化,elevation 海拔、深度,anisotropy 各向异性4.well drilling,drilling 钻井drilling site 井场seismic section 地震剖面water well 水井reserve pit 泥浆储备池cable tool drilling 顿钻rotary drilling 旋转钻井coiled-tubing drilling 连续油管钻井exploration well 勘探井wildcat well 野猫井appraisal well 评价井development well 开发井land drilling rig 陆上钻机off-shore drilling rig 海上钻机inclined well 斜井workover 修井derrick 井架hook 大钩elevator 吊卡traveling block 游动滑车wire line 钢丝绳crown block 天车draw works绞车mast 桅杆式井架rotary table 转盘kelly 方钻杆swivel 水龙头drill stem,drill string 钻柱kelly bushing方钻杆补心bit 钻头master bushing 转盘方补心mud 泥浆mud pump 泥浆泵mud pit 泥浆池standpipe 立柱collar 钻铤cuttings 岩屑rotary hose 旋转软管discharge line 出口管线standpipe 立管shale shaker 振动筛annulus 环空degasser 除气器desander 除砂器desilter 除泥器mud tank 泥浆罐mechanical power transmission 机械传动electric power transmission电力传动kick 井涌blowout 井喷blowout preventer(BOP)防喷器rig floor 钻台BOP stack 防喷器组choke manifold 地面节流管汇drag bit 切削钻头tri-cone bits 三牙轮钻头PDC bit 金刚石钻头steel-tooth rock bit 钢齿岩石钻头tungsten carbide insert bits 碳化钨钻头drill pipe 钻杆stabilizer 稳定器drilling fluid 钻井液oil-base mud 油基泥浆water-base mud 水基泥浆barite 重晶石vertical well 直井horizontal well 水平井deviated well 斜井directional well 定向井cluser well 丛式井Multilateral Well 多底井extended reach well 大位移井submerged barge 半潜式驳船tool pusher 钻井队长driller 司钻derrickman 井架工motorman 动力机工floorman 钻台工,场地工mudman 泥浆工5.well completion 完井cementing 注水泥,固井wellhead 井口conductor casing 导管surface casing 表层套管intermediate casing 中间套管,技术套管production casing 生产套管centralizer 扶正器scratcher 刮泥器guide shoe 引鞋jet-mixing hopper 给料器cementing head bottom plug 下塞slurry,cement slurry 水泥浆float collar浮箍top plug 上塞WOC(waiting on cement )水泥侯凝时间well logging,log 测井electrical log 电法测井wireline log 电缆测井radioactive log 放射性测井acoustic log 声波测井caliper log 井径测井dip log 倾角测井core 岩心coring 取心sidewall caring 井壁取心shaped-Charge 聚能射孔弹packer 封隔器christmas tree 采油树lifting equipment 举升设备well treatment 油井措施open hole completion 裸眼完井perforated completion 射孔完井slotted liner completion 割缝衬管完井gravel packed completion 砾石充填完井screen 筛管6. oil and gas production 油气生产,采油natural flow 自喷artificial lift 人工举升subsurface pump 深井泵gas lift 气举horizontal pipe flow 水平管流choke flow 嘴流wellbore multiphase flow 井筒多相管流porous media flow 多孔介质渗流inflow performance relationship (IPR)油井流入动态inflow performance relationship curve油井流入动态曲线,IPR曲线nodal systems analysis 节点系统分析flow pattern 流型vertical lift performance curve 流出动态曲线,VLP curvebubble flow 泡流slug or plug flow 段塞流churn flow 搅拌流annular flow 环流wispy annular flow 环雾状流mist flow 雾流liquid flow 纯液流slip effect 滑脱现象sucker rod pump 有杆泵progressive cavity pump 螺杆泵PCP subsurface hydraulic pump水力活塞泵electric submersible pumps电潜泵positive displacement pump 容积式泵plunger 活塞sucker rod 抽油杆upstroke 上冲程pumping unit抽油机sucker rod抽油杆horsehead 驴头standing valve 固定阀,吸入阀riding valve 排出阀walking beam pumping unit游梁式抽油机walking beam游梁Pitman连杆Crank 曲柄gear reducer变速箱prime mover 电动机,动力设备dynagraph card 示功图Progressive Cavity Pump(PCP ) 螺杆泵Subsurface Hydraulic Pump 水力活塞泵,射流泵Power fluid 动力液Electric Submersible Pump(ESP) 电潜泵7.Reservoir engineering 油藏工程primary recovery 一次采油secondary recovery 二次采油tertiary recovery 三次采油enhanced oil recovery (EOR)提高采收率Proven Reserves证实储量Probable Reserves概算储量Possible Reserves可能储量Solution-gas drive 溶解气驱Gas-cap drive 气顶驱Water drive 水驱Combination drive 混合驱Gravity-drainage drive 重力驱Edgewater drive 边水驱bottomwater drive 底水驱fingering 趾进water (gas) coning 水锥进/气锥进water cresting 水脊进water breakthrough 水突破watered out 水淹water flooding 注水peripheral flooding 外围注水line drive 排状注水five-spot pattern 五点井网seven-spot pattern 七点井网nine-spot pattern 九点井网inverted nine-spot pattern 反九点井网four-spot pattern 四点井网recovery efficiency 采收率pattern sweep efficiency 井网波及效率invasion efficiency 垂向波及效率Volumetric efficiency 体积波及效率areal efficiency 面积波及效率displacement efficiency 洗油效率mobility ratio 流度比well spacing 井距pattern geometry 井网类型chemical flooding 化学驱thermal recovery 热力采油miscible flooding 混相驱surfactant flooding 表面活性剂驱polymer flooding 聚合物驱caustic flooding 碱水驱in-situ combustion 火烧油层steam injection 注蒸汽热采wet combustion 湿式燃烧miscible slug process 混相段塞驱the enriched gas process富气驱the high-pressure lean gas process高压贫气驱the mutual solvent process互溶剂驱carbon dioxide process 二氧化碳驱microbial enhanced oil recovery 微生物采油。

陆相页岩油气水平井穿层体积压裂技术

陆相页岩油气水平井穿层体积压裂技术

doi:10.11911/syztjs.2023078引用格式:蒋廷学,肖博,沈子齐,等. 陆相页岩油气水平井穿层体积压裂技术[J]. 石油钻探技术,2023, 51(5):8-14.JIANG Tingxue, XIAO Bo, SHEN Ziqi, et al. Vertical penetration of network fracturing technology for horizontal wells in continental shale oil and gas [J]. Petroleum Drilling Techniques ,2023, 51(5):8-14.陆相页岩油气水平井穿层体积压裂技术蒋廷学1,2, 肖 博1,2, 沈子齐1,2, 刘学鹏1,2, 仲冠宇1,2(1. 页岩油气富集机理与高效开发全国重点实验室, 北京 102206;2. 中石化石油工程技术研究院有限公司, 北京 102206)摘 要: 针对陆相页岩油气储层纵向不同岩性夹层发育、黏土含量高等对压裂带来的挑战,研究提出了陆相页岩油气水平井穿层体积压裂技术。

该技术主要包括陆相页岩油气储层可压性评价、以预计最终可采储量(EUR )为目标的裂缝参数优化、以单簇裂缝模拟为基础的压裂施工参数优化、以提高远井缝高为基础的全程穿层压裂工艺优化、渗吸驱油一体化压裂液体系及性能评价和以渗吸机理为基础的压后闷井制度优化方法。

研究结果表明,陆相页岩油气压裂的裂缝复杂性程度普遍较低,要实现体积压裂应聚焦于压裂主裂缝的密切割和全程穿层压裂。

现场试验结果表明,穿层体积压裂技术可使产量提高20%以上,表明该技术具有推广应用价值。

关键词: 陆相;页岩油;页岩气;水平井;体积压裂;穿层;现场试验中图分类号: TE357.1 文献标志码: A 文章编号: 1001–0890(2023)05–0008–07Vertical Penetration of Network Fracturing Technology for Horizontal Wells inContinental Shale Oil and GasJIANG Tingxue 1,2, XIAO Bo 1,2, SHEN Ziqi 1,2, LIU Xuepeng 1,2, ZHONG Guanyu1,2(1. State Key Laboratory of Shale Oil and Gas Enrichment Mechanisms and Effective Development, Beijing, 102206, China ;2. Sinopec Research Institute of Petroleum Engineering Co., Ltd., Beijing, 102206, China )Abstract: In view of the challenges of many lithology interlayers vertically and high clay content in continental shale reservoirs, the vertical penetration of network fracturing technology for horizontal wells is proposed. This technology primarily includes the fracability evaluation of continental shale, optimization of fracture parameters for estimated ultimate recovery (EUR) maximization, optimization of fracturing treatment parameters based on single cluster fracture propagation simulation, optimization of whole-process vertical penetration of fracturing based on improving fracture height far from the borehole, development and evaluation the integrated fracturing fluid system with high imbibition and oil displacement efficiency, and optimization of post-fracturing shut-in period based on imbibition mechanisms, etc. The research results show that the complexity of fractures in continental shale oil and gas fracturing is generally low. To achieve network fracturing, the focus should be on the “dense cluster spacing ” fracturing and the vertical penetration fracturing throughout the whole process. The field tests show that the production by vertical penetration of network fracturing can be increased by more than 20%. Therefore, this technology has significant potential for widespread application.Key words: continental; shale oil; shale gas; horizontal well; network fracturing; vertical penetration; field test目前,随着国内页岩油气勘探开发进程的加快,陆相页岩油气逐渐成为新的油气产量增长点和研究热点[1–3],如渤海湾盆地济阳洼陷页岩油[4–10]、鄂尔多斯盆地庆城页岩油[11–12]、松辽盆地古龙凹陷页岩油[13–15]等。

契尔氏产品报价

契尔氏产品报价

天然泥土面膜Rare-Earth Face Masque(Oily/Acne) HK$155(4.2oz)
暗疮修护系列BLEMISH TREATMENT
草本去痘啫喱Blue Herbal Spot treatment HK$145(0.5oz)
暗疮修护膏Drawing Paste with Azulene HK$150(1oz)
茶树油修护化妆水(中偏油及油有暗疮)Tea Tree Oil Toner HK$265(8.4oz)
玫瑰清新化妆水(中偏油)Rosewater Facial Freshener and Toner HK$140(8.4oz)
蓝色草本爽肤水(油性及暗疮局部)Blue Astringent HK$100(4.2oz) HK$145(8.4oz)
Kiehl's契尔氏契尔氏浓缩蛋白素洗发水 Protein Concentrate Shampoo for Oil Hair 500ml HK¥240
"Kiehl's契尔氏全方位运动每天洗发水 All-Sport Everyday Shampoo 250ml HKD130
彩色润唇膏SPF15 Hue30G(黄金莓) Lip Balm SPF15 Hue30G(Golden Berry) HK$90 (0.5oz)
彩色润唇膏SPF15 Hue58B(黑莓) Lip Balm SPF15 Hue58B(Black Raspberry) HK$90 (0.5oz)
特效保湿霜Ultra Facial Cream HK$240 (1.7oz)
特效保湿乳液(中偏干至中偏油)Ultra Facial Moisturizer HK$130(2.5oz) HK$210(4.2oz)

CARBO陶瓷支撑剂

CARBO陶瓷支撑剂

CARBO Ceramics® proppant increases conductivity and improveseconomic performance.CARBO Ceramics and its predecessor companies have led the industry since ceramic proppant was first introduced in the 1970s for use in the hydraulic fracturing process. Today, CARBO has the mostextensive line of ceramic proppants, developed to optimize productivity and economic return in any type of oil or natural gas reservoir conditions.CARBO’s ceramic proppant yields measurably superior results versus inferior sand-based products, more than offsetting the incremental initial cost. Numerous case studies and field trials have consistently demonstrated:∙20% + increase in initial production rates.∙20% + increase in estimated ultimate recovery.∙Improved rates of return.∙Rapid payout on initial investment (often in just weeks or months).∙Lower finding and development costs for exploration and production companies.∙Accelerated recovery times.In addition, all of our ceramic proppant products are completely inert and environmentally friendly.With six manufacturing plants in the U.S., China and Russia, and a proven global distribution network, CARBO can quickly serve the needs of any customer anywhere in the world.In the Foundry, CARBO ACCUCAST® improves casting quality and lowers costs.CARBO ACCUCAST ceramic media has been engineered for superior performance.∙Higher precision and accuracy of castings, due to a lower thermal expansion.∙Lower scrap cost because of less wasted material.∙Reduced cost of correcting inaccuracies.∙Increased ability to produce thin wall castings because of greater flowability.∙Lower density than other specialty media, resulting in lower costs per cubic foot of product used.Why ceramic proppant?Increased productivity, economic benefit, increased ROI.The process of hydraulic fracturingOil and natural gas are typically contained in the pores of sedimentaryrock reservoirs thousands of feet underground. To access these reserves, wells are drilled into the rock formations, and a well is typically connected to the reservoir through a process called hydraulic fracturing.The hydraulic fracturing process consists of pumping fluids down a well at pressures sufficient to create fractures in the hydrocarbon-bearing rock formation. A granular material, called proppant, is transported in the fluid to fill the fracture, thus “propping” it open once high-pressure pumping stops. Theproppant-filled fracture creates a permeable channel through which the hydrocarbons can flow more freely, thereby increasing both production rates and the amount of oil or gas actually recovered from the well.The superiority of ceramicsSand and sand-based materials became the most popular type of proppant due to availability and low cost. However, a study of production rates published by the Society of Petroleum Engineers has shown that the additional strength and uniform size and shape of ceramic proppant provide higher performance than other types of proppant (SPE 77675). Wells that have been fractured with CARBO ceramic proppant consistently exhibit improved production of oil and gas in a variety of reservoir conditions.Optimizing production with Economic ConductivityUsing realistic downhole conditions helps maximize ROI.There are basic models used to try to determine a well’s production capacity given aparticular stimulation treatment. But the problem with simple models is that they are simply wrong.CARBO engineers have developed a sophisticated analysis that factors in complex variables and downhole conditions such as closure stress, non-darcy flow, multiphase flow, fluid velocity and cyclic stress to determine the realistic conductivity of the reservoir.The costs of hydraulic fracturing and other stimulation activities can then be assessed according to the corresponding increases in production, allowing producers to achieve the most cost-efficient production of oil and gas. This analysis is called Economic Conductivity.As an example, more than 100 field studies showed that optimizing the choice of proppant increased fracture conductivity and well productivity by 20 to 30%, as well as increasing the estimated ultimate recovery (EUR) by 30%.CARBO conducts Economic Conductivity analyses to individually optimize fracture treatments and deliver the best return on investment.For additional information, see the Economic Conductivity site at /.Getting the most out of any reservoirCARBO’s experience and expert ise are unmatched.CARBO Ceramics proppants are engineered to optimize conductivity in virtually anyapplication. No other manufacturer comes close to our comprehensive line ofhigh-quality products.Lightweight ceramic proppant for slickwater fracturingLow-cost, lightweight ceramic proppantLightweight, high-performance proppant, ideal for oil reservoirsIntermediate-strength proppant, frequently selected for moderate depth oil and gaswellsHigh-strength sintered bauxite proppant for deep and hostile downhole environmentsIdentifies the precise well or fracture stage that flows back proppantNon-Radioactive Traceable proppantResin-coated proppantResin-coated proppantCARBO BOND is engineered to control flowback of proppant into the wellbore from the fracture. The curable resin coating can be applied to any CARBO proppant. CARBO BOND effectively reduces costly clean-out issues in the wellbore by reducing effective stress on the proppant, providing encapsulation to maintain particle integrity and preventing fines from being released. It is formulated for maximum compatibility with today’s complicated fracturing fluids.FeaturesBonds in the fracture with temperature and closureResin coating completely encapsulates substrateBonded proppant pack reduces effective stress on proppantFormulated for maximum compatibility with complicated frac fluidsBenefitsVersatile – expands the usable application range (depth, temperature and stress)No proppant flowback – eliminates subsequent equipment damage, expense of cleanouts and disposalMaintains conductivity – resin coating prevents fines from being releasedMaintains particle integrity – prevents chemical attack on substrateNo additional chemical costs – since no fluid chemistry change is required, the job can be pumped as designedThe performance of CARBO BOND meets or exceeds that of any third-party coating, making CARBO Ceramics a single, trusted source for superior uncoated and resin-coated ceramic proppant.ProductsAll CARBO BOND proppants are engineered for high performance with proprietary resins, technology and coating process.The CARBO BOND family includes:Curable resin-coated ceramic proppantsCurable resin-coated sandPre-cured resin-coated sandCARBO BOND®LITE®: extending the lightweight advantageThe proprietary CARBO BOND LITE technology (curable resin-coated CARBO LITE® lightweight proppant) enhances and extends downhole application, allowing premium lightweight ceramic proppant to be used at greater well depths. CARBO BOND LITE proppant can be used in applications that previously required intermediate or high-density resin-coated ceramic proppant. CARBO BOND LITE also requires 17% less proppant by weight compared to resin-coated intermediate-density ceramic proppant.CARBO BOND®RCS: resin-coated sand with CARBO quality and expertiseCARBO BOND®RCS helps you achieve Economic Conductivity™ in an even wider range of reservoirs. CARBO BOND RCS features higher-conductivity Northern White sand, produced in CARBO’sstate-of-the-art coating facility. It is the only resin-coated sand that includes CARBO’s proven quality and outstanding tech support, all at a competitive price.CARBO BOND RCS (C) – with curable resin coatingCARBO BOND RCS (P) – with pre-cured resin coatingTank Top LinerThe integrity of every tank surface is critical.Corrosion and leaks in the top of a storage tank raise concerns associated with the Clean Air Act and animal cruelty.We can apply the Falcon Liner™ to the top of oil and gas storage tanks and extend the useful life of the tank without having to take the tank out of service.FeaturesModified polymer spray-on seamless liner.Impervious to low-acid chemical corrosion.Two-year limited warranty.Age-tested to 75+ years by an independent lab.AdvantagesThe tank does not have to come out of service.Falcon applies the tank top liner onsite.Falcon supplies a licensed safety inspector for projects requiring stand-by safety rescue.BenefitsA lower cost alternative to tank replacement.Falcon tank top liner requires no further maintenance or associated costs.Mitigates the risk of Clean Air Act violation.Tank LinerFalcon Technologies™ ends the concern over corroded, leaking tanks.One of the most common problems related to spill prevention, control and countermeasures (SPCC) regulations is storage tanks leaking due to surface corrosion or deteriorating seams.The innovative Falcon Liner™ is the most effective tank liner on the market. The spray-on modified polymer liner creates a seamless layer of protection that is not affected by the harsh chemicals encountered in oil and natural gas production and storage. The Falcon Liner has a scientifically tested useful life of 20+ years in a full immersion environment.FeaturesInnovative process produces a seamless, durable liner.The Falcon Liner is not affected by H2S or other harmful elements.Eighteen-month limited warranty.AdvantagesSpecially designed trailers provide service even in remote locations.Liner is installed by an experienced and highly skilled workforce.All tanks receive a three-point quality control inspection process following the Falcon Liner application.Turn-back times are generally the same day Falcon exits the tank.BenefitsProven technology prevents spills resulting from unpredictable tank erosion.The product is scientifically age-tested to 20+ years in a full immersion environment, dramatically extending the useful life of tanks and reducing replacement costs.Tank internal walls become virtually maintenance-free, eliminating costs.Fluid Tank TrucksThe Falcon Liner™ is ideally suited to a hostile, mobile environment.Tank trucks carrying crude oil, water or other low acid fluids pose particular challenges: rough road conditions that jar the tanks; temperature extremes; and internal pressures associated with expansion and contraction common to over-the-road activity.The Falcon Liner is superior under these adverse conditions. The spray-on modified polymer liner adheres well to aluminum and steel tanks. The flexibility and elasticity of the Falcon Liner enable it to withstand bending and flexing. The continuous, seamless application is particularly suited for the sharp angles and unusual shapes of mobile tanks.FeaturesModified polymer liner flexes with truck movement.Seamless application.Impervious to low acid concentration chemical corrosion.Abrasion resistant.AdvantagesFalcon Liner adheres to aluminum or steel tanks.Spray-on application provides continuous coverage on tank corners and angled seams.Modified polymer characteristics are suited to tank vibration, flexing and shocks.BenefitsElimination of leaks.Durability of Falcon Liner means longer life and lower replacement costs.Falcon Liner applies technology for long-lasting protectionInnovative process is quick, flexible, versatile and durable.The Falcon Liner is a sprayed-on modified polymer coating that adheres like glue to a variety of surfaces, providing a seamless, durable, maintenance-free layer of protection. It can be applied to new or existing tanks, bases, concrete revetments, and other equipment. The Falcon Liner is impervious to corrosion or damage due to chemicals or weather, virtually eliminating the risk of leaks or other environmental issues.Independent laboratory testing has shown that the Falcon Liner has a useful life of 75+ years. As a result, it dramatically extends asset life, resulting in reduced maintenance and replacement costs.The Falcon Liner is one of the best-performing products on the market as well as a highly cost-effective solution.Falcon Liner Products:Secondary ContainmentTank LinerTank BasesFluid Tank TrucksTank Top LinerTank Exchange ProgramSalt Water DisposalSurface Mounted Containment。

纳米颗粒尺寸、形状以及界面效应对介电和击穿场强等因素的影响

纳米颗粒尺寸、形状以及界面效应对介电和击穿场强等因素的影响

Society Chem.Mater.2010,22,1567–15781567DOI:10.1021/cm902852hNanoparticle,Size,Shape,and Interfacial Effects on Leakage Current Density,Permittivity,and Breakdown Strength of MetalOxide-Polyolefin Nanocomposites:Experiment and TheoryNeng Guo,†Sara A.DiBenedetto,†Pratyush Tewari,‡Michael nagan,*,‡Mark A.Ratner,*,†and Tobin J.Marks*,††Department of Chemistry and the Materials Research Center,Northwestern University,Evanston, Illinois60208-3113and‡Center for Dielectric Studies,Materials Research Institute,The Pennsylvania State University,University Park,Pennsylvania16802-4800Received September11,2009.Revised Manuscript Received December2,2009A series of0-3metal oxide-polyolefin nanocomposites are synthesized via in situ olefin polymeriza-tion,using the following single-site metallocene catalysts:C2-symmetric dichloro[rac-ethylenebisindenyl]-zirconium(IV),Me2Si(t BuN)(η5-C5Me4)TiCl2,and(η5-C5Me5)TiCl3immobilized on methylaluminoxane (MAO)-treated BaTiO3,ZrO2,3-mol%-yttria-stabilized zirconia,8-mol%-yttria-stabilized zirconia, sphere-shaped TiO2nanoparticles,and rod-shaped TiO2nanoparticles.The resulting composite materials are structurally characterized via X-ray diffraction(XRD),scanning electron microscopy(SEM), transmission electron microscopy(TEM),13C nuclear magnetic resonance(NMR)spectroscopy,and differential scanning calorimetry(DSC).TEM analysis shows that the nanoparticles are well-dispersed in the polymer matrix,with each individual nanoparticle surrounded by polymer.Electrical measurements reveal that most of these nanocomposites have leakage current densities of∼10-6-10-8A/cm2;relative permittivities increase as the nanoparticle volume fraction increases,with measured values as high as6.1. At the same volume fraction,rod-shaped TiO2nanoparticle-isotactic polypropylene nanocomposites exhibit significantly greater permittivities than the corresponding sphere-shaped TiO2nanoparticle-isotactic polypropylene nanocomposites.Effective medium theories fail to give a quantitative description of the capacitance behavior,but do aid substantially in interpreting the trends qualitatively.The energy storage densities of these nanocomposites are estimated to be as high as9.4J/cm3.IntroductionFuture pulsed-power and power electronic capacitors will require dielectric materials with ultimate energy storage den-sities of>30J/cm3,operating voltages of>10kV,and milli-second-microsecond charge/discharge times with reliable operation near the dielectric breakdown limit.Importantly, at2and0.2J/cm3,respectively,the operating characteristics of current-generation pulsed power and power electronic capacitors,which utilize either ceramic or polymer dielectric materials,remain significantly short of this goal.1An order-of-magnitude improvement in energy density will require the development of dramatically different types of materials, which substantially increase intrinsic dielectric energy den-sities while reliably operating as close as possible to the die-lectric breakdown limit.For simple linear response dielectric materials,the maximum energy density is defined in eq1,U e¼12εrε0E2ð1Þwhereεr is the relative dielectric permittivity,E the dielec-tric breakdown strength,andε0the vacuum permittivity (8.8542Â10-12F/m).Generally,metal oxides have large permittivities;however,they are limited by low breakdown fields.While organic materials(e.g.,polymers)can provide high breakdown strengths,their generally modest permit-tivities have limited their application.1Recently,inorganic-polymer nanocomposite materials have attracted great interest,because of their potential for high energy densities.2By integrating the complementary*Authors to whom correspondence should be addressed.E-mail addresses: mxl46@(M.T.L.),ratner@(M.A.R.),and t-marks@(T.J.M.).(1)(a)Pan,J.;Li,K.;Li,J.;Hsu,T.;Wang,Q.Appl.Phys.Lett.2009,95,022902.(b)Claude,J.;Lu,Y.;Li,K.;Wang,Q.Chem.Mater.2008, 20,2078–2080.(c)Chu,B.;Zhou,X.;Ren,K.;Neese,B.;Lin,M.;Wang,Q.;Bauer,F.;Zhang,Q.M.Science2006,313,334–336.(d) Cao,Y.;Irwin,P.C.;Younsi,K.IEEE Trans.Dielectr.Electr.Insul.2004,11,797–807.(e)Nalwa,H.S.,Ed.Handbook of Low and High Dielectric Constant Materials and Their Applications;Academic Press:New York,1999;V ol.2.(f)Sarjeant,W.J.;Zirnheld,J.;MacDougall,F.W.IEEE Trans.Plasma Sci.1998,26,1368–1392.(2)(a)Kim,P.;Doss,N.M.;Tillotson,J.P.;Hotchkiss,P.J.;Pan,M.-J.;Marder,S.R.;Li,J.;Calame,J.P.;Perry,J.W.ACS Nano 2009,3,2581–2592.(b)Li,J.;Seok,S.I.;Chu,B.;Dogan,F.;Zhang, Q.;Wang,Q.Adv.Mater.2009,21,217–221.(c)Li,J.;Claude,J.;Norena-Franco,L.E.;Selk,S.;Wang,Q.Chem.Mater.2008,20, 6304–6306.(d)Gross,S.;Camozzo,D.;Di Noto,V.;Armelao,L.;Tondello,E.Eur.Polym.J.2007,43,673–696.(e)Gilbert,L.J.;Schuman,T.P.;Dogan,F.Ceram.Trans.2006,179,17–26.(f)Rao,Y.;Wong,C.P.J.Appl.Polym.Sci.2004,92,2228–2231.(g)Dias,C.J.;Das-Gupta,D.K.IEEE Trans.Dielectr.Electr.Insul.1996,3,706–734.(h)Mammone,R.R.;Binder,M.Novel Methods For Preparing Thin,High Permittivity Polymerdielectrics for Capacitor Applica-tions;Proceedings of the34th International Power Sources Symposium, 1990,Cherry Hill,NJ;IEEE:New York,1990;pp395-398./cmPublished on Web01/05/2010 r2010American Chemical1568Chem.Mater.,Vol.22,No.4,2010Guo et al.properties of their constituents,such materials can simul-taneously derive high permittivity from the inorganic in-clusions and high breakdown strength,mechanical flexibility,facile processability,light weight,and tunability of the properties(polymer molecular weight,comonomer incorporation,viscoelastic properties,etc.)from the poly-mer host matrix.3In addition,convincing theoretical argu-ments have been made suggesting that large inclusion-matrix interfacial areas should afford greater polarization levels,dielectric response,and breakdown strength.4 Inorganic-polymer nanocomposites are typically pre-pared via mechanical blending,5solution mixing,6in situ radical polymerization,7and in situ nanoparticle syn-thesis.8However,host-guest incompatibilities intro-duced in these synthetic approaches frequently result in nanoparticle aggregation and phase separation over largelength scales,9which is detrimental to the electrical prop-erties of the composite.10Covalent grafting of the poly-mer chains to inorganic nanoparticle surfaces has alsoproven promising,leading to more effective dispersionand enhanced electrical/mechanical properties;11how-ever,such processes may not be optimally cost-effective,nor may they be easily scaled up.Furthermore,thedevelopment of accurate theoretical models for the di-electric properties of the nanocomposite must be accom-panied by a reliable experimental means to achievenanoparticle deagglomeration.In the huge industrial-scale heterogeneous or slurryolefin polymerization processes practiced today,SiO2isgenerally used as the catalyst support.12Very large localhydrostatic pressures arising from the propagating poly-olefin chains are known to effect extensive SiO2particlefracture and lead to SiO2-polyolefin composites.12Based on this observation,composite materials with enhancedmechanical properties13have been synthesized via in situpolymerizations using filler surface-anchored Ziegler-Natta or metallocene polymerization catalysts.14There-fore,we envisioned that processes meditated by rationallyselected single-site metallocene catalysts supported onferroelectric oxide nanoparticles15might disrupt ubiqui-tous and problematic nanoparticle agglomeration,16toafford homogeneously dispersed nanoparticles within thematrix of a processable,high-strength commodity poly-mer,already used extensively in energy storage capaci-tors.17Moreover,we envisioned that the methylalumino-xane(MAO)co-catalyst14i layer applied to the metaloxide nanoparticle surfaces would,after polymer workupunder ambient conditions,serve as an effective precursorfor a thin Al2O3layer to moderate the large anticipated(3)(a)Nelson,J.K.;Hu,Y.J.Phys.D:Appl.Phys.2005,38,213–222.(b)Tanaka,T.;Montanari,G.C.;M€u lhaupt,R.IEEE Trans.Dielectr.Electr.Insul.2004,11,763–784.(c)Lewis,T.J.IEEE Trans.Dielectr.Electr.Insul.1994,15,812–825.(d)Newnham,R.E.Annu.Rev.Mater.Sci.1986,16,47–68.(4)(a)Saha,S.K.Phys.Rev.B2004,69,1254161–125464.(b)Nelson,J.K.;Utracki,L.A.;MacCrone,R.K.;Reed,C.W.IEEE Conf.Electr.Insul.Dielectr.Phenomena2004,314–317.(c)Li,J.Phys.Rev.Lett.2003,90,217601/1–4.(5)(a)Subodh,G.;Deepu,V.;Mohanan,P.;Sebastian,M.T.Appl.Phys.Lett.2009,95,062903.(b)Dang,Z.;Wu,J.;Fan,L.;Nan,C.Chem.Phys.Lett.2003,376,389–394.(6)(a)Goyal,R.K.;Jagadale,P.A.;Mulik,U.P.J.Appl.Polym.Sci.2009,111,2071–2077.(b)Afzal,A.B.;Akhtar,M.J.;Nadeem,M.;Hassan,M.M.J.Phys.Chem.C2009,113,17560–17565.(c)Huang, X.Y.;Jiang,P.K.;Kim,C.U.J.Appl.Phys.2007,102,124103.(d) Parvatikar,N.;Ambika Prasad,M.V.N.J.Appl.Polym.Sci.2006, 100,1403–1405.(e)Badheka,P.;Magadala,V.;Gopi Devaraju,N.;Lee,B.I.;Kim,E.S.J.Appl.Polym.Sci.2006,99,2815–2821.(f)Xie, S.;Zhu,B.;Xu,Z.;Xu,Y.Mater.Lett.2005,59,2403–2407.(g) Schroeder,R.;Majewski,L.;Grell,M.Adv.Mater.2005,17,1535–1539.(h)Bai,Y.;Cheng,Z.;Bharti,V.;Xu,H.;Zhang,Q.Appl.Phys.Lett.2000,76,3804–3806.(7)(a)Andou,Y.;Jeong,J.-M.;Nishida,H.;Endo,T.Macromolecules2009,42,7930–7935.(b)Thomas,P.;Dwarakanath,K.;Varma,K.B.R.Synth.Met.2009,159,2128–2134.(c)Chen,Y.-M.;Lin,H.-C.;Hsu,R.-S.;Hsieh,B.-Z.;Su,Y.-A.;Sheng,Y.-J.;Lin,J.-J.Chem.Mater.2009,21,4071–4079.(d)He,A.;Wang,L.;Li,J.;Dong,J.;Han,C.C.Polymer2006,47,1767–1771.(e)Ginzburg,V.V.;Myers, K.;Malowinski,S.;Cieslinski,R.;Elwell,M.;Bernius,M.Macro-molecules2006,39,3901–3906.(f)Mizutani,T.;Arai,K.;Miyamoto, M.;Kimura,Y.J.Appl.Polym.Sci.2006,99,659–669.(g)Xiao,M.;Sun,L.;Liu,J.;Li,Y.;Gong,K.Polymer2002,43,2245–2248.(h)R.Popielarz,R.;Chiang,C.K.;Nozaki,R.;Obrzut,J.Macromolecules 2001,34,5910–5915.(8)(a)Balan,L.;Jin,M.;Malval,J.-P.;Chaumeil,H.;Defoin,A.;Vidal,L.Macromolecules2008,41,9359–9365.(b)Lu,J.;Moon,K.S.;Xu,J.;Wong,C.P.J.Mater.Chem.2006,16,1543–1548.(c)Yogo, T.;Yamamoto,T.;Sakamoto,W.;Hirano,S.J.Mater.Res.2004,19, 3290–3297.(9)(a)Vaia,R.A.;Maguire,J.F.Chem.Mater.2007,19,2736–2751.(b)Mackay,M.E.;Tuteja,A.;Duxbury,P.M.;Hawker,C.J.;Van Horn,B.;Guan,Z.;Chen,G.;Krishnan,R.S.Science2006,311,1740–1743.(c)Lin,Y.;Boeker,A.;He,J.;Sill,K.;Xiang,H.;Abetz,C.;Li,X.;Wang,J.;Emrick,T.;Long,S.;Wang,Q.;Balazs,A.;Russell,T.P.Nature2005,434,55–59.(10)(a)Stoyanov,H.;Mc Carthy,D.;Kollosche,M.;Kofod,G.Appl.Phys.Lett.2009,94,232905.(b)Chen,G.;Davies,A.E.IEEE Trans.Dielectr.Electr.Insul.2000,7,401–407.(c)Khalil,M.S.IEEE Trans.Dielectr.Electr.Insul.2000,7,261–268.(11)(a)Zhang,Y.;Ye,Z.Macromolecules2008,41,6331–6338.(b)Maliakal,A.;Katz,H.E.;Cotts,P.M.;Subramoney,S.;Mirau,P.J.Am.Chem.Soc.2005,127,14655–14662.(c)Rusa,M.;Whitesell,J.K.;Fox,M.A.Macromolecules2004,37,2766–2774.(d)Bartholome,C.;Beyou,E.;Bourgeat-Lami,E.;Chaumont,P.;Zydowicz,N.Macro-molecules2003,36,7946–7952.(e)Corbierre,M.K.;Cameron,N.S.;Sutton,M.;Mochrie,S.G.J.;Lurio,L.B.;R€u hm,A.;Lennox,R.B.J.Am.Chem.Soc.2001,123,10411–10412.(f)von Werne,T.;Patten,T.E.J.Am.Chem.Soc.2001,123,7497–7505.(g)Nuss,S.;B€o ttcher,H.;Wurm,H.;Hallensleben,M.L.Angew.Chem.,Int.Ed.2001,40, 4016–4018.(12)(a)Kaminsky,W.;Funck,A.;Wiemann,K.Macromol.Symp.2006,239,1–6.(b)Li,K.-T.;Kao,Y.-T.J.Appl.Polym.Sci.2006,101, 2573–2580.(c)du Fresne von Hohenesche,C.;Unger,K.K.;Eberle,T.J.Mol.Catal.A:Chem.2004,221,185–199.(d)Fink,G.;Steinmetz,B.;Zechlin,J.;Przybyla,C.;Tesche,B.Chem.Rev.2000,100,1377–1390.(13)(a)Dubois,P.;Alexandre,M.;J e r^o me,R.Macromol.Symp.2003,194,13–26.(b)Kaminsky,W.Macromol.Chem.Phys.1996,197, 3907–3945.(14)For recent reviews of single-site olefin polymerization,see:(a)Amin,S.B.;Marks,T.J.Angew.Chem.,Int.Ed.2008,47,2006–2025.(b)Marks,T.J.,ed.Proc.Natl.Acad.Sci.,U.S.A.,2006,103, 15288-15354,and contributions therein(Special Feature on Poly-merization).(c)Suzuki,anomet.Chem.2005,8,177–216.(d)Alt,H.G.Dalton Trans.2005,20,3271–3276.(e)Kaminsky,W.J.Polym.Sci.Polym.Chem.2004,42,3911–3921.(j)Wang,W.;Wang, L.J.Polym.Mater.2003,20,1–8.(f)Delacroix,O.;Gladysz,J.A.mun.2003,6,665–675.(g)Kaminsky,W.;Arndt-Rosenau, M.Applied Homogeneous Catalysis with Organometallic Com-pounds,2nd Edition;Wiley-VCH Verlag GmbH:Weinheim, Germany,2002.(h)Lin,S.;Waymouth,R.M.Acc.Chem.Res.2002,35,765–773.(i)Chen,E.Y.-X.;Marks,T.J.Chem.Rev.2000,100,1391–1434.(15)For recent reviews of single-site heterogeneous catalysis,see:(a)Thomas,J.M.;Raja,R.;Lewis,D.W.Angew.Chem.,Int.Ed.2005, 44,6456–6482.(b)Cop e ret,C.;Chabanas,R.;Petroff Saint-Arroman, R.;Basset,J.-M.Angew.Chem.,Int.Ed.2003,42,156–181.(c) Hlatky,G.G.Chem.Rev.2000,100,1347–1376.(d)Reven,L.J.Mol.Catal.1994,86,447–477.(16)Kim,P;Jones,S.C.;Hotchkiss,P.J.;Haddock,J.N.;Kippelen,B.;Marder,S.R.;Perry,J.W.Adv.Mater.2007,19,1001–1005. (17)Rabuffi,M.;Picci,G.IEEE Trans.Plasma Sci.2002,30,1939–1942.Article Chem.Mater.,Vol.22,No.4,20101569polyolefin -ferroelectric permittivity contrast.If too large,such contrasts are associated with diminished breakdown strength and suppressed permittivity.18,19In a brief preliminary communication,we reported evidence that high-energy-density BaTiO 3-and TiO 2-isotactic polypropylene nanocomposites could be pre-pared via in situ propylene polymerization mediated by anchoring/alkylating/activating C 2-symmetric dichloro-[rac -ethylenebisindenyl]zirconium(IV)(EBIZrCl 2)on the MAO-treated oxide nanoparticles (see Scheme 1).20The resulting nanocomposites were determined to have rela-tively uniform nanoparticle dispersions and to support remarkably high projected energy storage densities ;as high as 9.4J/cm 3,as determined from permittivity and dielectric breakdown measurements.In this contribution,we significantly extend the inorganic inclusion scope to include a broad variety of nanoparticle types,to investi-gate the effects of nanoparticle identity and shape on the electrical/dielectric properties of the resulting nanocom-posites,and to compare the experimental results with theoretical predictions.We also extend the scope of metallocene polymerization catalysts (see Chart 1)and olefinic monomers,with the goal of achieving nanocom-posites that have comparable or potentially greater pro-cessability and thermal stability.Here,we present a full discussion of the synthesis,microstructural and electrical characterization,and theoretical modeling of these nano-composites.It will be seen that nanoparticle coating with MAO and subsequent in situ polymerization are crucial to achieving effective nanoparticle dispersion,and,simul-taneously,high nanocomposite breakdown strengths (as high as 6.0MV/cm)and high permittivities (as high as 6.1)can be realized to achieve energy storage densities as high as 9.4J/cm 3.Experimental SectionI.Materials and Methods.All manipulations of air-sensitive materials were performed with rigorous exclusion of O 2and moisture in flamed Schlenk-type glassware on a dual-manifold Schlenk line or interfaced to a high-vacuum line (10-5Torr),or in a dinitrogen-filled MBraun glovebox with a high-capacity recirculator (<1ppm O 2and H 2O).Argon (Airgas,pre-purified),ethylene (Airgas,polymerization grade),and propy-lene (Matheson or Airgas,polymerization grade)were purified by passage through a supported MnO oxygen-removal column and an activated Davison 4A molecular sieve column.Styrene (Sigma -Aldrich)was dried sequentially for a week over CaH 2and then triisobutylaluminum,and it was freshly vacuum-transferred prior to polymerization experiments.The monomer 1-octene (Sigma -Aldrich)was dried over CaH 2and was freshly vacuum-transferred prior to polymerization experiments.To-luene was dried using activated alumina and Q-5columns,according to the method described by Grubbs,21and it was additionally vacuum-transferred from Na/K alloy and stored in Teflon-valve sealed bulbs for polymerization experiments.Ba-TiO 3and TiO 2nanoparticles were kindly provided by Prof.Fatih Dogan (University of Missouri,Rolla)and Prof.Thomas Shrout (Penn State University),respectively.20ZrO 2nanopar-ticles were purchased from Sigma -Aldrich.The reagents 3-mol %-yttria-stabilized zirconia (TZ3Y)and 8-mol %-yttria-stabilized zirconia (TZ8Y)nanoparticles were purchased from Tosoh,Inc.TiO 2nanorods were purchased from Reade Ad-vanced Materials (Riverside,RI).All of the nanoparticles were dried in a high vacuum line (10-5Torr)at 80°C overnight to remove the surface-bound water,which is known to affect the dielectric breakdown performance adversely.22The deuteratedScheme 1.Synthesis of Polyolefin -Metal OxideNanocompositesChart 1.Metallocene polymerization catalysts andMAO.(18)(a)Li,J.Y.;Zhang,L.;Ducharme,S.Appl.Phys.Lett.2007,90,132901/1–132901/3.(b)Li,J.Y .;Huang,C.;Zhang,Q.M.Appl.Phys.Lett.2004,84,3124–3126.(19)Cheng,Y.;Chen,X.;Wu,K.;Wu,S.;Chen,Y.;Meng,Y.J.Appl.Phys.2008,103,034111/1–034111/8.(20)Guo,N.;DiBenedetto,S.A.;Kwon,D.-K.;Wang,L.;Russell,M.T.;Lanagan,M.T.;Facchetti,A.;Marks,T.J.J.Am.Chem.Soc.2007,129,766–767.(21)Pangborn,A.B.;Giardello,M.A.;Grubbs,R.H.;Rosen,R.K.;Timmers,anometallics 1996,15,1518–1520.(22)(a)Hong,T.P.;Lesaint,O.;Gonon,P.IEEE Trans.Dielectr.Electr.Insul.2009,16,1–10.(b)Ma,D.;Hugener,T.A.;Siegel,R.W.;Christerson,A.;M artensson,E.;€Onneby,C.;Schadler,L.S.Nano-technology 2005,16,724–731.(c)Ma,D.;Siegel,R.W.;Hong,J.;Schadler,L.S.;M artensson,E.;€Onneby,C.J.Mater.Res.2004,19,857–863.1570Chem.Mater.,Vol.22,No.4,2010Guo et al. solvent1,1,2,2-tetrachloroethane-d2was purchased fromCambridge Isotope Laboratories(g99at.%D)and was usedas-received.Methylaluminoxane(MAO;Sigma-Aldrich)waspurified by removing all the volatiles in vacuo from a1.0Msolution in toluene.The reagents dichloro[rac-ethylenebisin-denyl]zirconium(IV)(EBIZrCl2),and trichloro(pentamethyl-cyclopentadienyl)titanium(IV)(Cp*TiCl3)were purchasedfrom Sigma-Aldrich and used as-received.Me2Si(t BuN)(η5-C5Me4)TiCl2(CGCTiCl2)was prepared according to publishedprocedures.23nþ-Si wafers(root-mean-square(rms)roughnessof∼0.5nm)were obtained from Montco Silicon Tech(SpringCity,PA),and aluminum substrates were purchased fromMcMaster-Carr(Chicago,IL);both were cleaned according to standard procedures.24II.Physical and Analytical Measurements.NMR spectra were recorded on a Varian Innova400spectrometer(FT400 MHz,1H;100MHz,13C).Chemical shifts(δ)for13C spectra were referenced using internal solvent resonances and are reported relative to tetramethylsilane.13C NMR assays of polymer microstructure were conducted in1,1,2,2-tetrachlor-oethane-d2containing0.05M Cr(acac)3at130°C.Resonances were assigned according to the literature for isotactic polypro-pylene,poly(ethylene-co-1-octene),and syndiotactic polystyr-ene,respectively(see more below).Elemental analyses were performed by Midwest Microlabs,LLC(Indianapolis,IN). Inductively coupled plasma-optical emission spectroscopy (ICP-OES)analyses were performed by Galbraith Laboratories, Inc.(Knoxville,TN).Powder X-ray diffraction(XRD)patterns were recorded on a Rigaku DMAX-A diffractometer with Ni-filtered Cu K R radiation(λ=1.54184A).Pristine ceramic nanoparticles and composite microstructures were examined with a FEI Quanta sFEG environmental scanning electron microscopy(SEM)system with an accelerating voltage of30 kV.Transmission electron microscopy(TEM)was performed on a Hitachi Model H-8100TEM system with an accelerating voltage of200kV.Samples for TEM imaging were prepared by dipping a TEM grid into a suspension of nanocomposite powder in acetone.Polymer composite thermal transitions were mea-sured on a temperature-modulated differential scanning calori-meter(TA Instruments,Model2920).Typically,ca.10mg of samples were examined,and a ramp rate of10°C/min was used to measure the melting point.To erase thermal history effects, all samples were subjected to two melt-freeze cycles.The data from the second melt-freeze cycle are presented here.III.Electrical Measurements.Metal-insulator-metal (MIM)or metal-insulator-semiconductor(MIS)devices for nanocomposite electrical measurements were fabricated by first doctor-blading nanocomposite films onto aluminum(MIM)or nþ-Si(MIS)substrates,followed by vacuum-depositing top gold electrodes through shadow masks.Specifically,a clean substrate was placed on a hot plate heated to just below the polymer-nanocomposite melting point.A small amount of the polymer nanocomposite powder was placed in the center of the substrate and left until the powder began to melt.Once in this phase,the polymer nanocomposite is spread over the center of the sub-strate using a razor blade.The sample was removed from the heat,cooled,and then pressed in a benchtop press to ensure uniform film thicknesses and smooth surfaces.Gold electrodes 500A thick were vacuum-deposited directly on the films through shadow masks that defined a series of different areas (0.030,0.0225,0.01,0.005,and0.0004cm2)at3Â10-6Torr(at 0.2-0.5A/s).Electrical properties of the films were character-ized by two probe current-voltage(I-V)measurements using a Keithley Model6430Sub-Femtoamp Remote Source Meter, operated by a local LABVIEW program.Triaxial and low triboelectric noise coaxial cables were incorporated with the Keithley remote source meter and Signatone(Gilroy,CA)probe tip holders to minimize the noise level.All electrical measure-ments were performed under ambient conditions.For MIS devices,the leakage current densities(represented by the symbol J,given in units of A/cm2)were measured with positive/negative polarity applied to the gold electrode to ensure that the nþ-Si substrate was operated in accumulation.A delay time of1s was incorporated into the source-delay-measure cycle to settle the source before recording currents.Capacitance measurements of the MIM and MIS structures were performed with a two-probe digital capacitance meter(Model3000,GLK Instruments,San Diego,CA)at(5and24kHz.Several methods have been developed to measure the dielectric breakdown strength of polymer and nanocomposite films.1a,25In this study,various methods were examined(e.g.,pull-down electrodes25),and the two-probe method was used to collect the present data because the top gold electrodes had already been deposited for leakage current and capacitance measurements.The dielectric break-down strength of the each type of composite film was measured in a Galden heat-transfer fluid bath at room temperature with a high-voltage amplifier(Model TREK30/20A,TREK,Inc., Medina,NY)with a ramp rate of1000V/s.26The thicknesses of the dielectric films were measured with a Tencor P-10step profilometer,and these thicknesses were used to calculate the dielectric constants and breakdown strengths of the film sam-ples(see Table2,presented later in this work).IV.Representative Immobilization of a Metallocene Catalyst on Metal Oxide Nanoparticles.In the glovebox,2.0g of BaTiO3 nanoparticles,200mg of MAO,and50mL of dry toluene were loaded into a predried100-mL Schlenk reaction flask,which was then attached to the high vacuum line.Upon stirring,the mixture became a fine slurry.The slurry was next subjected to alternating sonication and vigorous stirring for2days with constant removal of evolving CH4.Next,the nanoparticles were collected by filtration and washed with fresh toluene(50mLÂ4) to remove any residual MAO.Then,200mg of metallocene catalyst EBIZrCl2and50mL of toluene were loaded in the flask containing the MAO-coated nanoparticles.The color of the nanoparticles immediately became purple.The slurry mixture was again subjected to alternating sonication and vigorous Table1.XRD Linewidth Analysis Results for the Oxide-PolypropyleneNanocompositespowder2θ(deg)full width athalf maximum,fwhm(deg)crystallitesize,L(nm)a BaTiO331.4120.25435.6 BaTiO3-polypropylene31.6490.27132.8 TiO225.3600.31727.1 TiO2-polypropylene25.3580.36123.5a Crystallite size(L)is calculated using the Scherrer equation:L=0.9λ/[B(cosθB)whereλis the X-ray wavelength,B the full width at half maximum(fwhm)of the diffraction peak,andθB the Bragg angle.(23)Stevens,J.C.;Timmers,F.J.;Wilson,D.R.;Schmidt,G.F.;Nickias,P.N.;Rosen,R.K.;Knight,G.W.;Lai,S.Eur.Patent Application EP416815A2,1991.(24)Yoon,M.-H.;Kim,C.;Facchetti,A.;Marks,T.J.J.Am.Chem.Soc.2006,128,12851–12869.(25)Claude,J.;Lu,Y.;Wang,Q.Appl.Phys.Lett.2007,91,212904/1–212904/3.(26)Gadoum,A.;Gosse,A.;Gosse,J.P.Eur.Polym.J.1997,33,1161–1166.Article Chem.Mater.,Vol.22,No.4,20101571stirring overnight.The nanoparticles were then collected by filtration and washed with fresh toluene until the toluene remained colorless.The nanoparticles were dried on the high-vacuum line overnight and stored in a sealed container in the glovebox at-40°C in darkness.V.Representative Synthesis of an Isotactic Polypropylene Nanocomposite via In Situ Propylene Polymerization.In the glovebox,a250-mL round-bottom three-neck Morton flask, which had been dried at160°C overnight and equipped with a large magnetic stirring bar,was charged with50mL of dry toluene,200mg of functionalized nanoparticles,and50mg of MAO.The assembled flask was removed from the glovebox and the contents were subjected to sonication for30min with vigorous stirring.The flask was then attached to a high vacuum line(10-5Torr),the catalyst slurry was freeze-pump-thaw degassed,equilibrated at the desired reaction temperature using an external bath,and saturated with1.0atm(pressure control using a mercury bubbler)of rigorously purified propylene while being vigorously stirred.After a measured time interval,the polymerization was quenched by the addition of5mL of methanol,and the reaction mixture was then poured into800 mL of methanol.The composite was allowed to fully precipitate overnight and was then collected by filtration,washed with fresh methanol,and dried on the high vacuum line overnight to constant weight.VI.Representative Synthesis of a Poly(ethylene-co-1-octene) Nanocomposite via In Situ Ethyleneþ1-Octene Copolymeriza-tion.In the glovebox,a250-mL round-bottom three-neck Morton flask,which had been dried at160°C overnight and equip-ped with a large magnetic stirring bar,was charged with50mL of dry toluene,200mg of functionalized nanoparticles,and 50mg of MAO.The assembled flask was removed from the glo-vebox and the contents were subjected to sonication for30min with vigorous stirring.The flask was then attached to a high vacuum line(10-5Torr),the catalyst slurry was freeze-pump-thaw degassed,equilibrated at the desired reaction temperature using an external bath,and saturated with1.0atm(pressure control using a mercury bubbler)of rigorously purified ethylene while being vigorously stirred.Next,5mL of freshly vacuum-transferred1-octene was quickly injected into the rapidly stirred flask using a gas-tight syringe equipped with a flattened spraying needle.After a measured time interval,the polymerization was quenched by the addition of5mL of methanol,and the reaction mixture was then poured into800mL of methanol.The com-posite was allowed to fully precipitate overnight and was then collected by filtration,washed with fresh methanol,and dried on the high vacuum line overnight to constant weight.Film fabri-cation of the composite powders into thin films for MIS electrical testing was unsuccessful due to the high incorporation level of1-octene.VII.Representative Synthesis of a Syndiotactic Polystyrene Nanocomposite via In Situ Styrene Polymerization.In the glove-box,a250-mL round-bottom three-neck Morton flask,which had been dried at160°C overnight and equipped with a large magnetic stirring bar,was charged with50mL of dry toluene, 200mg of functionalized nanoparticles,and50mg of MAO.The assembled flask was removed from the glovebox and the con-tents were subjected to sonication for30min with vigorous stirring.The flask was then attached to a high vacuum line(10-5 Torr)and equilibrated at the desired reaction temperature usingTable2.Electrical Characterization Results for Metal Oxide-Polypropylene Nanocomposites aentry compositenanoparticlecontent b(vol%)melting temperature,T m c(°C)permittivity dbreakdownstrength e(MV/cm)energy density,U f(J/cm3)1BaTiO3-iso PP0.5136.8 2.7(0.1 3.1 1.2(0.1 2BaTiO3-iso PP0.9142.8 3.1(1.2>4.8>4.0(0.6 3BaTiO3-iso PP 2.6142.1 2.7(0.2 3.9 1.8(0.2 4BaTiO3-iso PP 5.2145.6 2.9(1.0 2.7 1.0(0.3 5BaTiO3-iso PP 6.7144.8 5.1(1.7 4.1 3.7(1.2 6BaTiO3-iso PP13.6144.8 6.1(0.9>5.9>9.4(1.37s TiO2-iso PP g0.1135.2 2.2(0.1>2.8>0.8(0.1 8s TiO2-iso PP g 1.6142.4 2.8(0.2 4.1 2.1(0.2 9s TiO2-iso PP g 3.1142.6 2.8(0.1 2.8 1.0(0.1 10s TiO2-iso PP g 6.2144.8 3.0(0.2 4.7 2.8(0.211r TiO2-iso PP h 1.4139.7 3.4(0.3 1.00.40(0.35 12r TiO2-iso PP h 3.0142.4 4.1(0.70.90.22(0.09 13r TiO2-iso PP h 5.1143.7 4.9(0.40.90.23(0.0814ZrO2-iso PP 1.6142.9 1.7(0.3 1.50.1815ZrO2-iso PP 3.9145.2 2.0(0.4 1.90.3216ZrO2-iso PP7.5144.9 4.8(1.1 1.00.2017ZrO2-iso PP9.4144.4 6.9(2.6 2.0 1.02(0.7318TZ3Y-iso PP 1.1142.9 1.1(0.1N/A N/A19TZ3Y-iso PP 3.1143.5 1.8(0.2N/A N/A20TZ3Y-iso PP 4.3143.8 2.0(0.2N/A N/A21TZ3Y-iso PP 6.7144.9 2.7(0.2N/A N/A22TZ8Y-iso PP0.9142.9 1.4(0.1 3.8 1.07(0.04 23TZ8Y-iso PP 2.9143.2 1.8(0.1 2.80.5924TZ8Y-iso PP 3.8143.2 2.0(0.2 2.00.4125TZ8Y-iso PP 6.6146.2 2.4(0.4 2.20.61a Polymerizations performed in50mL of toluene under1.0atm of propylene at20°C.b From elemental analysis.c From differential scanning calorimetry(DSC).d Derived from capacitance measurements.e Calculated by dividing the breakdown voltage by the film thickness,which is measured using a Tencor p10profilometer.f Energy density(U)is calculated from the following relation:U=0.5ε0εr E b2,whereε0is the permittivity of a vacuum,εr the relative permittivity,and E b the breakdown strength.g The superscripted prefix“s”denotes sphere-shaped TiO2nanoparticles.h The superscripted prefix“r”denotes rod-shaped TiO2nanoparticles.。

答案-新闻翻译-兰蔻产品

答案-新闻翻译-兰蔻产品

Regulators warned L'Oreal, the world's biggest cosmetics group, to stop advertising skincare products using language that makes them sound like drugs.The U.S. Food and Drug Administration said Lancome USA, a L'Oreal unit, claimed some of its skin creams could "boost the activity of genes" or "stimulate cell regeneration" to reduce signs of aging.Any product that is intended to affect the structure or function of the human body is classified as a drug, the FDA said, according to a warning letter posted on its website on Tuesday.Companies are not allowed to sell drugs in the United States without submitting an application to the FDA proving their products are safe and effective and then winning FDA approval.The FDA said failure to fix the advertising claims could lead to enforcement actions, such as seizure of the products and injunctions against their manufacturers and distributors.兰蔻产品广告遭美药监局警告FDA warns L'Oreal about drug-like claims for anti-aging creams美国食品药品监督管理局日前对法国欧莱雅集团发出警告,要求其下属的兰蔻美国分公司停止在兰蔻系列护肤品广告中使用类似药品功效的描述语言。

中国页岩气开发经济评价方法探索_孔令峰

中国页岩气开发经济评价方法探索_孔令峰
3 中国页岩气开发项目经济评价方法探索
3.1 以平台为单位开展经济评价更适合页岩气开发特点 蜀南地区某区块页岩气开发方案参照地质条件类似的
Haynesville项目,采用丛式井组开发[11],单井初期产量、 递减率、单井最终可采储量等主要指标参照Haynesville盆 地页岩气开发项目设计。但因项目没有充分的生产数据支 持,诸多假设与实际情况可能有较大出入。主要体现在: 一是假设所有目的层页岩气资源丰度、压力系数等主要参 数基本一致,未考虑不同平台所辖页岩气资源差异状况。 二是假设每个平台上所有页岩气井投产压力和初期产量基 本相同,递减规律也保持一致,实际上平台之间和单井之 间差异很大。三是页岩气单位操作成本参照四川盆地常规 气田平均操作成本取值,对中后期排液采气和增压开采成 本考虑不足。四是预测页岩气井生产时间可以长达20年, 但实际上15年后单井产量可能已降至很低的水平,或者操 作成本已经过高,很难有继续开井生产的价值。五是按照 常规气田开发直线法计提折耗。对于井口定压生产、单井 没有稳产期的页岩气井,按照产量法计提折耗更符合实际 情况,更有利于尽快回收投资。
2 中国开展页岩气开发项目经济评价面临的难题
页岩气属于非常规天然气资源,必须采用非常规的理 念才能实现规模有效开发。页岩气开发属于技术和资金密 集型产业,技术要求和单位资金投入远高于常规天然气资 源开发。其开发生产的特点也与常规天然气差异较大,对 页岩气开发项目的经济评价方法与参数需要进行针对性的 选择和调整。
1 中美页岩气开发现状和行业综合发展环境对比
1.1 中国目前仍处于页岩气勘探开发的早期阶段 美国是全球页岩气开发的先行者,2014年其页岩气
(干气)产量超过3700亿立方米。2015年6月,国土资源 部《中国页岩气资源调查报告(2014年)》[2]指出“我国 页岩气资源潜力巨大,富集规律不清,可采资源尚未真 正落实;勘查开发点上取得重大突破,核心技术尚需攻 关。”2014年,中国页岩气产量为13亿立方米。国家能源 局预测中国2015年页岩气产量将达到65亿立方米,2020 年可达到300亿立方米[3]。但业界并不乐观,认为受多重因 素的影响,到“十三五”末中国页岩气产量或许难以达到 100亿立方米。中国页岩气发展无论从规模上还是开发水 平上都处于勘探开发的早期阶段。
  1. 1、下载文档前请自行甄别文档内容的完整性,平台不提供额外的编辑、内容补充、找答案等附加服务。
  2. 2、"仅部分预览"的文档,不可在线预览部分如存在完整性等问题,可反馈申请退款(可完整预览的文档不适用该条件!)。
  3. 3、如文档侵犯您的权益,请联系客服反馈,我们会尽快为您处理(人工客服工作时间:9:00-18:30)。

SPE 147623Estimated Ultimate Recovery (EUR) as a Function of Production Practicesin the Haynesville ShaleV. Okouma, F. Guillot, M. Sarfare, Shell Canada Energy, V. Sen, Taurus Reservoir Solutions Ltd.,D. Ilk, DeGolyer and MacNaughton, T.A. Blasingame, Texas A&M UniversityCopyright 2011, Society of Petroleum EngineersThis paper was prepared for presentation at the SPE Annual Technical Conference and Exhibition held in Denver, Colorado, USA, 30 October–2 November 2011.This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written consent of the Society of Petroleum Engineers is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright. AbstractRecent developments in well completion technologies have transformed the unconventional reservoir systems into economically feasible reservoirs. However, the uncertainty associated with production forecasts and non-uniqueness related with well/reservoir parameter estimation, are the main issues in future development of these reservoirs. In addition, recent operational methods such as restricting rates by decreasing the choke size add up to the uncertainty in production forecasts. This work attempts to investigate the effect of production practices on ultimate recovery. It is observed that wells producing in the Haynesville shale gas play exhibit severe productivity loss throughout their producing life. Production practices such as controlling the drawdown or restricting rates by decreasing the choke size are employed by several operators to deal with the severe productivity loss. In this work our main objective is to investigate the issues (such as stress dependent permeability, proppant embedment, operational problems, etc.)contributing to decreasing well productivity over time. In particular, from modeling standpoint, we focus on stress-dependent permeability as a mechanism, which affects well performance over time.Using a horizontal well with multiple fractures numerical simulation model coupled with geomechanics, we generate synthetic simulation cases including several drawdown scenarios. It is shown that high drawdown cases result in higher effective stress fields around the well and fracture system. We therefore infer that higher effective stress fields result in lower well productivity over time. Based on this hypothesis and diagnostics of field data, we model two different scenarios (i.e., high drawdown and low drawdown cases) for a horizontal well with multiple fractures using two different permeability decay functions and same well/formation model parameters. Our modelling results indicate that low drawdown case yields higher recovery suggesting that rate restriction could be a mitigating factor in decreasing well productivity over time.IntroductionHydrocarbon production from unconventional reservoir systems (e.g., tight gas sands, shale gas, tight/shale oil, etc.) has become significant in recent years due to recent advances in the technology allowing to drill and complete wells in these complex reservoir systems at lower costs. The developments in the technology to develop and produce complex unconventional reservoir systems such as shale gas reservoirs bring the difficulties and uncertainty associated with well performance. The uncertainty is mainly due to the lack of our complete understanding of the production mechanisms and behavior of these reservoir systems. And the difficulty is therefore associated with establishing the long term production decline in these reservoirs.In simple terms this study focuses on the factors affecting well performance and productivity in the Haynesville shale. Significant amount of natural gas has been produced from the Haynesville shale since 2008 and the Haynesville shale is considered as one of the largest natural gas fields in the United States. The Haynesville shale is a black, organic rich shale of Upper Jurassic age located in east Texas and northwest Louisiana, which is deposited with mainly heavier clay minerals, silica, and calcite. The depth of the Haynesville shale ranges from approximately 10,000 ft in the northwest part to 14,000 ft in the southeast (Buller et al. 2010). It is overpressured with pressure gradients higher than 0.9 psi/ft. Due to high reservoir pressure of the Haynesville shale, production practices has been shifted to control drawdown or to restrict the rates by the operators to avoid any damage occuring in the well/reservoir during production.。

相关文档
最新文档