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1.发明授权公开(公告)号：US06730812B2
公开(公告)日：2004-05-04
申请号：US10358552
申请日：2003-02-05
IPC分类号： C07F954
CPC分类号： C07C17/2635 , C07C1/34 , C07F9/5352 , C07F9/54 , C07C25/24
摘要： The present invention provides a method of preparing a phosphonium salt of the formula [R1R2R3P—CR4R5R6]X, comprising ball-milling a phosphine of the formula R1R2R3P with a compound of the formula XCR4R5R6; a method of preparing a phosphorus ylide of the formula R1R2R3P═CR4R5, comprising ball-milling a phosphonium salt of the formula [R1R2R3P—HCR4R5]X in the presence of a base; and a method of preparing an olefin of the formula R4R5C═CR7H or R4R5C═CR7R8, comprising ball-milling a phosphorus ylide of the formula R1R2R3P═CR4R5 with a compound of the formula R7C(O)H or R7C(O)R8. The inventive method produces phosphonium salts and phosphorus ylides by mechanical processing solid reagents under solvent-free conditions. The advantages of the present invention over conventional solution methods, include: (1) extremely high selectivity; (2) high yields; (3) low processing temperatures; (4) simple and scalable reactions using commercially available equipment; and (5) the complete elimination of solvents from the reaction.
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2.发明授权公开(公告)号：US06773692B2
公开(公告)日：2004-08-10
申请号：US10167556
申请日：2002-06-12
IPC分类号： C01B304
CPC分类号： F17C11/005 , C01B3/0005 , C01B3/04 , H01M8/065 , Y02E60/321 , Y02E60/324 , Y02E60/364
摘要： The present invention provides a cost-effective method of producing pure hydrogen gas from hydride-based solid materials. The hydride-based solid material is mechanically processed in the presence of a catalyst to obtain pure gaseous hydrogen. Unlike previous methods, hydrogen may be obtained from the solid material without heating, and without the addition of a solvent during processing. The described method of hydrogen production is useful for energy conversion and production technologies that consume pure gaseous hydrogen as a fuel.
摘要翻译： 本发明提供了一种从氢化物基固体材料生产纯氢气的成本有效的方法。 氢化物基固体材料在催化剂的存在下机械加工以获得纯的气态氢。 与以前的方法不同，可以在不加热的情况下从固体材料获得氢，并且在加工期间不加入溶剂。 所描述的氢气生产方法对于消耗纯气态氢作为燃料的能量转化和生产技术是有用的。
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3.发明授权Active magnetic refrigerants based on Gd-Si-Ge material and refrigeration apparatus and process 失效基于Gd-Si-Ge材料的主动磁性制冷剂及制冷装置及工艺
公开(公告)号：US5743095A
公开(公告)日：1998-04-28
申请号：US753064
申请日：1996-11-19
CPC分类号： H01F1/015 , F25B21/00 , H01F1/0009 , F25B2321/0022 , Y02B30/66 , Y10S505/889 , Y10S505/891
摘要： Active magnetic regenerator and method using Gd.sub.5 (Si.sub.x Ge.sub.1-x).sub.4, where x is equal to or less than 0.5, as a magnetic refrigerant that exhibits a reversible ferromagnetic/antiferromagnetic or ferromagnetic-II/ferromagnetic-I first order phase transition and extraordinary magneto-thermal properties, such as a giant magnetocaloric effect, that renders the refrigerant more efficient and useful than existing magnetic refrigerants for commercialization of magnetic regenerators. The reversible first order phase transition is tunable from approximately 30 K to approximately 290 K (near room temperature) and above by compositional adjustments. The active magnetic regenerator and method can function for refrigerating, air conditioning, and liquefying low temperature cryogens with significantly improved efficiency and operating temperature range from approximately 10 K to 300 K and above. Also an active magnetic regenerator and method using Gd.sub.5 (Si.sub.x Ge.sub.1-x).sub.4, where x is equal to or greater than 0.5, as a magnetic heater/refrigerant that exhibits a reversible ferromagnetic/paramagnetic second order phase transition with large magneto-thermal properties, such as a large magnetocaloric effect that permits the commercialization of a magnetic heat pump and/or refrigerant. This second order phase transition is tunable from approximately 280 K (near room temperature) to approximately 350 K by composition adjustments. The active magnetic regenerator and method can function for low level heating for climate control for buildings, homes and automobile, and chemical processing.
摘要翻译： 主动磁再生器和使用Gd5（SixGe1-x）4的方法，其中x等于或小于0.5，作为表现出可逆铁磁/反铁磁性或铁磁性II /铁磁体I一阶相变和非凡磁体的磁性制冷剂 - 诸如巨磁电效应的热特性，其使制冷剂比现有的用于磁性再生器商业化的磁性制冷剂更有效和有用。 可逆的一阶相变可以通过组合调整从大约30K到大约290K（接近室温）可调。 主动式蓄热器和方法可以在制冷，空调和液化低温制冷剂方面发挥作用，其效率和工作温度范围从大约10K到300K以上。 作为磁化加热器/制冷剂，使用Gd5（SixGe1-x）4，其中x等于或大于0.5的主动磁性再生器和方法也表现出具有大的磁热特性的可逆铁磁/顺磁二阶相变， 例如允许磁热泵和/或制冷剂商业化的大的磁热效应。 该二阶相变可通过组合调整从约280K（近室温）调节至约350K。 主动式蓄热器和方法可用于建筑物，家庭和汽车以及化学处理的低温加热用于气候控制。
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4.发明授权公开(公告)号：US07549296B2
公开(公告)日：2009-06-23
申请号：US11061141
申请日：2005-02-18
CPC分类号： F25B9/145 , F25B2309/003 , F25B2309/1415
摘要： A multi-stage cryocooler having a relatively low temperature stage to cool to less than about 15K and having a regenerator including a ductile intermetallic compound including one or more rare earth elements and one or more non-rare earth metals.
摘要翻译： 具有相对较低温度阶段以冷却至小于约15K并具有包括包含一种或多种稀土元素和一种或多种非稀土金属的延性金属间化合物的再生器的多级低温冷却器。
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公开(公告)号：US5887449A
公开(公告)日：1999-03-30
申请号：US881836
申请日：1997-06-25
CPC分类号： F25B21/00 , F25J1/001 , F25J1/0225 , H01F1/015 , F25B2321/002 , F25J2270/908 , Y02B30/66
摘要： A dual stage active magnetic regenerator refrigerator as well as method using the Joule-Brayton thermodynamic cycle includes a high temperature stage refrigerant comprising DyAl.sub.2 or (Dy.sub.1-x Er.sub.x)Al.sub.2 where x is selected to be greater than 0 and less than about 0.3 in combination with a low temperature stage comprising (Dy.sub.1-x Er.sub.x)Al.sub.2 where x is selected to be greater than about 0.5 and less than 1 to provide significantly improved refrigeration efficiency in the liquefaction of gaseous hydrogen.
摘要翻译： 双级主动式蓄冷器冷冻机以及使用焦耳 - 布莱顿热力循环的方法包括包含DyAl 2或（Dy 1-x Er x）Al 2的高温级制冷剂，其中x选择为大于0且小于约0.3， 包括（Dy1-xErx）Al2的低温阶段，其中x被选择为大于约0.5且小于1，以提供气态氢液化中显着提高的制冷效率。
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6.发明授权Method of making active magnetic refrigerant materials based on Gd-Si-Ge alloys 有权基于Gd-Si-Ge合金制备主动磁性制冷剂材料的方法公开(公告)号：US07114340B2
公开(公告)日：2006-10-03
申请号：US10413417
申请日：2003-04-14
CPC分类号： C22C28/00 , F25B21/00 , H01F1/0009 , H01F1/015 , Y02B30/66 , Y10S505/889 , Y10S505/89 , Y10S505/891
摘要： An alloy made of heat treated material represented by Gd5(SixGe1−x)4 where 0.47≦x≦0.56 that exhibits a magnetic entropy change (−ΔSm) of at least 16 J/kg K, a magnetostriction of at least 2000 parts per million, and a magnetoresistance of at least 5 percent at a temperature of about 300K and below, and method of heat treating the material between 800 to 1600 degrees C. for a time to this end.
摘要翻译： 由Gd 5（Si x Si 1-x S）4表示的热处理材料制成的合金，其中0.47 表现出至少16J / kgK的磁熵变（-DeltaSmΠ），至少2000ppm的磁致伸缩和至少5的磁阻的<= x <= 0.56 在约300K及以下的温度下的百分比，以及在800至1600摄氏度之间热处理该材料的方法一段时间。
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公开(公告)号：US06318090B1
公开(公告)日：2001-11-20
申请号：US09395423
申请日：1999-09-14
IPC分类号： F25B900
CPC分类号： F25B9/14 , F25B2309/003
摘要： A cryocooler with a regenerator comprising one or more regenerator components, which are ductile and oxidation resistant, including a rare earth metal, an alloy of two or more rare earth metals, an alloy of a rare earth metal with a non-rare earth metal, and an alloy of a rare earth metal with at least one interstitial element.
摘要翻译： 一种具有再生器的低温冷却器，其包括一种或多种具有延展性和抗氧化性的再生器组分，包括稀土金属，两种或更多种稀土金属的合金，稀土金属与非稀土金属的合金， 以及稀土金属与至少一种间隙元素的合金。
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8.发明授权
公开(公告)号：US5537826A
公开(公告)日：1996-07-23
申请号：US266090
申请日：1994-06-27
CPC分类号： F25B9/14 , H01F1/015 , F02G2242/42 , F25B2309/003
摘要： A two stage Gifford-McMahon cryocooler having a low temperature stage for reaching approximately 10K, wherein the low temperature stage includes a passive magnetic heat regenerator selected from the group consisting of Er.sub.6 Ni.sub.2 Sn, Er.sub.6 Ni.sub.2 Pb, Er.sub.6 Ni.sub.2 (Sn.sub.0.75 Ga.sub.0.25), and Er.sub.9 Ni.sub.3 Sn comprising a mixture of Er.sub.3 Ni and Er.sub.6 Ni.sub.2 Sn in the microstructure.
摘要翻译： 具有低温阶段达到约10K的两级吉福德 - 麦克马洪低温制冷机，其中低温级包括选自Er6Ni2Sn，Er6Ni2Pb，Er6Ni2（Sn0.75Ga0.25）和Er9Ni3Sn的无源磁热蓄热器，其包含 Er3Ni和Er6Ni2Sn在微结构中的混合物。
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公开(公告)号：US20120315182A1
公开(公告)日：2012-12-13
申请号：US13506434
申请日：2012-04-18
申请人： Karl A. Gschneider, JR. , Frederick A. Schmidt , Alexandra O. Tsokol , Vitalij K. Pecharsky , Lawrence L. Jones , Paul B. Wheelock
发明人： Karl A. Gschneider, JR. , Frederick A. Schmidt , Alexandra O. Tsokol , Vitalij K. Pecharsky , Lawrence L. Jones , Paul B. Wheelock
CPC分类号： C22C28/00 , B22F9/20 , C22C1/0491 , C22C27/04 , H01F1/015
摘要： A method for preparing R5X4 alloy materials where R is a rare earth element selected from one or more of La, Ce, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Lu, Sc, and Y and X represents a non-rare earth alloying element such as silicon, germanium, tin, lead, gallium, indium and mixtures thereof. The method involves carbothermically reducing amounts of a rare earth element-containing oxide, an alloying element-containing oxide and/or alloying element in elemental or alloy form, and carbon at elevated temperature to form an R5X4 alloy material, which is melted, solidified, and optionally heat treated. Such a method provides an economical and efficient technique of configuring magnetic refrigerant, magnetostrictive and magnetoresistive alloys and products.
摘要翻译： 一种制备R5X4合金材料的方法，其中R是选自La，Ce，Sm，Eu，Gd，Tb，Dy，Ho，Er，Tm，Lu，Sc和Y中的一种或多种的稀土元素，X和X表示 非稀土合金元素如硅，锗，锡，铅，镓，铟及其混合物。 该方法包括在元素或合金形式的碳纳米管中减少含稀土元素的氧化物，含合金元素的氧化物和/或合金元素的量，并在升高的温度下形成碳，以形成熔融固化的R 5 X 4合金材料， 并任选地进行热处理。 这种方法提供了一种经济有效的配置磁性制冷剂，磁致伸缩和磁阻合金和产品的技术。
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10.发明授权Method of making active magnetic refrigerant, colossal magnetostriction and giant magnetoresistive materials based on Gd-Si-Ge alloys 失效基于Gd-Si-Ge合金制备主动磁致冷剂，巨磁致伸缩和巨磁阻材料的方法公开(公告)号：US06589366B1
公开(公告)日：2003-07-08
申请号：US09793822
申请日：2001-02-23
IPC分类号： H01F1053
CPC分类号： C22C28/00 , F25B21/00 , H01F1/0009 , H01F1/015 , Y02B30/66
摘要： Method of making an active magnetic refrigerant represented by Gd5(SixGe1−x)4 alloy for 0≦x≦1.0 comprising placing amounts of the commercially pure Gd, Si, and Ge charge components in a crucible, heating the charge contents under subambient pressure to a melting temperature of the alloy for a time sufficient to homogenize the alloy and oxidize carbon with oxygen present in the Gd charge component to reduce carbon, rapidly solidifying the alloy in the crucible, and heat treating the solidified alloy at a temperature below the melting temperature for a time effective to homogenize a microstructure of the solidified material, and then cooling sufficiently fast to prevent the eutectoid decomposition and improve magnetocaloric and/or the magnetostrictive and/or the magnetoresistive properties thereof.
摘要翻译： 制备由Gd5（SixGe1-x）4合金表示的0 <= x <= 1.0的活性磁性制冷剂的方法，包括将商业纯的Gd，Si和Ge电荷组分的量放置在坩埚中，加热次级 压力达到合金的熔融时间足以使合金均匀化并且存在于Gd电荷组分中的氧氧化碳以减少碳，迅速凝固坩埚中的合金，并在低于该温度的温度下热处理该固化的合金 熔融温度有效均匀化固化材料的微观结构，然后充分快速冷却以防止共析分解并改善磁热和/或磁致伸缩和/或磁阻特性。
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