CN1128566C - 聚合物浸渍的加热元件和支承骨架和电阻加热元件的制造方法 - Google Patents
聚合物浸渍的加热元件和支承骨架和电阻加热元件的制造方法 Download PDFInfo
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Abstract
本发明提供电阻加热元件,含有这种元件的热水器和制备这种元件的方法。电阻加热元件可通过水箱壁设置以便加热流体如水。该元件包括一个在其上具有第一支承面(69)的支承骨架(70)。还包括卷绕在第一支承面(69)上并最好与至少一对终端端部连接的电阻丝(66)。支承骨架(70)和电阻丝(66)然后被气密地封装并电绝缘在一个导热的聚合物覆盖层(64)内。支承骨架(70)可改善封装电阻丝(66)时的注射模塑操作,并能具有可用来提高导热率的热传递翅片(62)。
Description
本申请为1994.12.29立案、题为“浸渍加热元件和电阻加热材料及在其上沉积的聚合物层”的美国专利申请序号08/365,920的继续。
本发明涉及电阻加热元件,更具体点说,涉及用来加热气体和液体的、聚合物基的电阻加热元件。
用于热水器的电阻加热元件在传统上是由金属和陶瓷构件制成的,其典型构造包括一对接线端销铜焊到Ni-Cr线圈的端头上,然后沿轴向布置使它通过一个U形管状金属套。电阻线圈用陶瓷材料粉末(通常为氧化镁)与金属套绝缘。
虽然这种传统的电阻加热元件历年来被电热水器工业用作役马,但它具有多个广泛公认的缺点。例如,在金属套和水箱任何暴露金属表面之间会产生直流电流,从而能使系统内的各种阳极金属构件腐蚀。典型地为铜或铜合金的加热元件的金属套还会从水中吸引石灰沉积,导致加热元件的早期失效。另外,由于铜价历年来递增,采用黄铜配件和铜管件的代价递增。
作为金属元件的替代,至少有一个塑料套的电热元件曾在Cunningham的美国专利3,943,328号中提出,在所公开的装置中,传统的电阻丝和氧化镁粉与塑料套结合使用。由于塑料套不导电,不会和加热单元中与水箱内水接触的其他金属零件形成原电池,也不会有石灰沉积。但不幸的是,由于各种原因,这种现有技术塑料套的加热元件未能在正常的使用寿命期内达到高的额定功率,从而没有被广泛接受。
本发明提供的电阻加热元件能够通过水箱壁如热水器的存储箱壁设置以便用来加热流体介质。该元件包括一个在其上具有第一支承表面的支承骨架,能对流体进行电阻加热的电阻丝卷绕在这个支承表面上。电阻丝在一导热的聚合物覆盖层内被气密地封装并电绝缘。
本发明由于设有支承电阻加热丝的轻巧骨架结构可使模塑操作大为方便。这个结构包括多个开口或孔眼使熔化的聚合物材料能更好地流动。敞开的支承提供更容易充填的较大的模型横截面。例如在注射模塑时,熔化的聚合物能被导引到差不多整个电阻加热丝的周围,这样在支承骨架和聚合物覆盖模塑层的界面上气泡的发生可大大减少。已知这种气泡当元件在水中操作时会造成热点。另外,轻巧的支承骨架可减少模塑构件的分层和电阻加热丝从聚合物覆盖层上分离的潜在危险。本发明所提供的方法可大大改进覆盖层并且由于只需较低的压力可有助于缩小模型的开口。
本发明的另一个实施例提供了电阻加热元件的一种制造方法。该制造方法包括提供一个具有支承表面的支承骨架,将电阻加热丝卷绕在支承表面上。最后将导热的聚合物模塑在电阻加热丝的外面,使加热丝电绝缘并被气密地封装。这个方法可被改变为,注射模塑出支承骨架和导热的聚合物,然后再在这两个构件上施加一层公用的树脂,使得出的元件具有更均匀的导热率。
附图阐明本发明的较优实施例和要公开的其他资料,其中:
图1为本发明的较优的聚合物的流体加热器的透视图;
图2为图1中的聚合物流体加热器左侧的平面图;
图3为图1的聚合物流体加热器前面的平面图,包括部分剖视图和剥去外皮的视图;
图4为图1中的聚合物流体加热器的较优的内部模型部的前面的平面图,包括剖视图;
图5为图1中的聚合物流体加热器的较优的端部组合件的前平面图和部分剖视图;
图6为本发明的聚合物流体加热器的较优的线圈端的放大的部分前平面图;
图7为本发明的聚合物流体加热器的双线圈实施例的放大的部分前平面图;
图8为本发明的加热元件的较优的支承骨架的前透视图;
图9为图8中较优的支承骨架的放大的部分视图,图中示出沉积的导热聚合物的覆盖层;
图10为另一种支承骨架的放大的剖视图;
图11为图10中支承骨架的侧平面图;及
图12为图10中的完整的支承骨架的前平面图。
本发明提供电阻加热元件和含有这些元件的热水器。这些装置在减少热水器和热油器的直流电流腐蚀石灰沉积和元件寿命短促的问题上是有效的。如同本文所用,名词“流体”和“流体介质”兼指液体和气体。
参阅附图,特别是图1-3,其中示出本发明的较优的聚合物流体加热器100,该加热器含有导电的电阻加热材料,其形式例如可为丝、网、带或蛇形物。在该较优的加热器100中,线圈14具有一对自由端连接到一对接线端12和16上以资产生电阻加热。线圈14被气密地并在电气上与流体绝缘且具有一层成为整体的高温聚合物材料。换句话说,起作用的电阻加热材料被聚合物覆盖层保护着使它不能在流体中发生短路。本发明的电阻材料具有足够的表面面积、长度和剖面厚度,可将水加热到至少约120°F的温度而不会熔化聚合物层。如从下面的论述可知,这可通过仔细地选择适当的材料及其尺寸来做到。
具体参阅图3,较优的聚合物流体加热器100一般具有三个整体部件:一个接线端组合件200如图5所示,一个内部模型件300如图4所示,和一个聚合物覆盖层30。下面继续说明这些亚构件中的每一件及其装到聚合物流水加热器100中的最终组合件。
图4所示的较优内部模型件300为一由高温聚合物制成的单个注射模塑件。内部模型件300最好在其最外端设有一个突缘32。与突缘32邻接为一具有多道螺纹22的轴套部。螺纹22被设计为与通过存储水箱如热水器水箱13侧壁的安装孔的内直径配合。O型环(未示出)可用在突缘32的内侧表面上借以提供较为可靠的水密密封。较优的内部模型件300还包括一个位在其较优的圆形横截面内的热控管空腔39。热控管空腔39可包括一个端壁33用来使热控管25与流体隔离。热控管空腔39最好通过突缘32敞开使接线端组合件200容易插入。较优的内部模型件300还含有至少一对导电体空腔31和35位在热控管空腔和内部模塑件的外壁之间以便用来接纳导电汇流条18和接线端组合件200的接线端导电线20。内部模型件300在其外周面上设有一连串的径向对齐槽38,这些槽可能是螺线槽或不连接的沟槽等,并应充分间隔开以便使所提供的线座在电气上将较优线圈14的螺旋线隔开。
较优的内部模型件300可用注射模塑法制出。流动通过的空腔11最好用一12.5英寸长的液压作用的型芯拉棒制出,从而造成一个约为13-18英寸长的元件。内部模型件300可被填充在采用设在突缘32对面的环形流道的金属模型内。起作用的元件部分10的目标壁厚希望小于0.5英寸,最好小于0.1英寸,目标范围约为0.04-0.06英寸,该值据信是注射模塑设备目前能做到的下限。还有一对钩或销45和55也在起作用元件展开部10上模塑出来位在接续的螺线槽或沟槽之间以便为一个或多个线圈的螺旋形提供一个接线端点或锚固点。在注射模塑时可采用通过突缘部的侧向型芯拉棒和端向型芯拉棒来制出热控管空腔39、流动通过空腔11、导电体空腔31和35和流动通过孔57。
参阅图5,现在说明较优的接线端组合件200。该组合件200具有一个聚合物端盖28,它被设计用来接纳一对接线端连接件23和24。如图2所示,接线端连接件23和24可含有螺孔34和36以便用来接纳带螺纹的连接件如螺钉从而安装外部电线。接线端连接件23和24为接线端导电线20和热控管导电汇流条21的端部。热控管汇流条21以热控管接线端27在电路上与接线端连接件24连接。另一热控管接线端29被连接到热控管导电汇流条18上,该汇流条被设计为可配合在沿着图4下部延伸的导电体空腔35内。为了完成回路,设有热控管25。这里您可任意选择,也可不用热控管,而用恒温器、固态的TCO(限时断路继电器)、或者仅用一条连接到外部断路器上的接地的带、或其他。据信接地带(未示出)可位在与一个接线端端部16或12接近之处,这样在聚合物熔化时便会短路。
在较优的环境中,热控管25可用一个按压作用的恒温器/热保护器如同Porfage电气公司出售的型式M系列。这种热保护器具有紧凑的尺寸适宜用于120/240V的AC载荷。它具有一个导电的双金属构造和一个电工上常用的箱,端盖28最好为一分开模塑的聚合物零件。
在接线端组合件200和内部模型件300制造好以后,它们最好先装配在一起,然后再将外露的线圈14卷绕在起作用的元件部分10的对齐的槽38上。在这样做的时候,必须小心以便用线圈的接线端端部12和16构成一个完整的回路。这一点可通过将线圈接线端端部12和16铜焊、锡焊或点焊到接线端导电线20和热控管导电汇流排18上来做到。同样重要的是,在敷设聚合物覆盖层之前应先恰当地将线圈14定位在内部模型件300上。在较优的实施例中,聚合物覆盖层30是挤压出来而形成的热塑性的聚合物与内部模型件300的结合。如同内部模型件那样,在模塑过程中可将型芯拉棒插入到模型内借以使流动通过孔眼57和流动通过空腔11保持敞开。
现在看图6和7,其中示出本发明的聚合物电阻加热元件的单根和双根的电阻丝实施例。在图6所示的单线实施例中,内部模型件300的对齐槽38被用来将具有螺旋线42和43的第一线对卷绕成线圈状。由于该较优实施例包括一根叠合的电阻丝,叠合线的端部或螺旋线的接线端44只要环绕销钉45弯曲就可套在销钉45上。销钉45理想的做法是内部模型件300的一个部分,可在内部模型件300上注射模塑出来。
与此类似,还可有双根电阻丝的设计。在这实施例中,第一根电阻丝的第一对螺旋线42和43与同一根电阻丝的下一接续对的螺旋线46和47被卷绕在第二销钉55上的第二线圈的螺旋线接线端54隔开。在螺旋线46和47之后,将第二根电阻丝的在电路上与第二线圈的螺旋线接线端连通的螺旋线52和53卷绕在内部模型件300的下一邻接对的对齐槽内。虽然这里所示双线圈组合件为每根线有一对螺旋线交替排列,但应知道,如果需要,每根电阻丝也可以两个或多个螺旋线为一组排列,或者按不规则的数目的螺旋线和卷绕形状卷绕,只要其导电线圈相互间被内部模型件或某些其他的绝缘材料如分开的塑料覆盖层等保持绝缘即可。
本发明的塑料零件最好具有“高温”聚合物,它在流体介质温度约为120-180°F时不会显著地变形或熔化。熔点大于200°F的热塑性聚合物最为合适,但某些陶瓷和热固性聚合物也可用于这个目的。较优的热塑性材料可包括:碳氟化合物、聚芳基砜、聚酰亚胺、聚醚酮醚、对聚苯硫、聚醚基砜及这些热塑性塑料的混合物和共聚物。对包括某些环氧、酚和硅氧烷的应用,热固性聚合物可被接受。液晶聚合物也可应用,它可改善高温时的化学过程。
在本发明的较优实施例中,对聚苯硫(PPS)最为合适,因为它能用在高温下、费用低并较易加工,特别是在注射模塑时。
本发明的聚合物可含有约为5-40重量%的增强纤维如石墨、玻璃或尼龙纤维。这些聚合物可与各种添加剂混合借以改善导热和脱模性能。添加碳、石墨和金属粉末或鳞片可提高导热率。但重要的是,这些添加剂都不能过量使用,因为过多的任何一种导电材料都可以损害较优的聚合物覆盖层的绝缘和抗腐蚀的效果。本发明的任何一个聚合物的元件都可用这些材料的任何一种组合来制成,取决于该元件的终极用途。
用来在本发明的流体加热器中传导电流并产生热的电阻材料最好为一种导电而耐热的电阻金属。通用的金属为Ni-Cr合金,但某些铜、钢和不锈钢合金也可适用。另外可以预见的是含有石墨、碳或金属粉末或纤维的导电聚合物,例如,它们可用来作为金属电阻材料的替代物,只要它们能产生足够的电阻热来加热如水的流体即可。较优聚合物流体加热器100的其余导电体也可用这些导电材料制造。
作为本发明的较优内部模型件300的替代,图8和9示出的支承骨架70已被证实能提供另外的好处。当一固体的内部模型件300如一根管子被应用在注射模塑的操作中时,由于加热器的设计要求像0.025英寸那样小的壁厚,和可达14英寸的异常长度,有时会发生模型不恰当地被充填的情况。导热聚合物还有一个问题是,它适宜含有添加剂如玻璃纤维和陶瓷粉、氧化铝(Al2O3)和氧化镁(MgO),但这些添加剂会使熔化的聚合物变得极其粘稠。结果需要过量的压力才能恰当地充填模型,并且这种压力有时会使模型开启。
为了减少这些问题的发生,本发明考虑采用了一种具有多个开口和一个用来保持电阻加热丝66的支承表面的支承骨架70。在一较优的实施例中,支承骨架70包括一个管状件,其上设有大约6-8个互相间隔开在骨架70整个长度上延伸的纵长键槽69。这些键槽69被一连串在管状件的长度上沿纵向间隔开的支承环60夹持在一起。这些支承环60适宜小于约0.05英寸的厚度,并且较好约为0.025-0.030英寸的厚度。键槽69最好在顶部约为0.125英寸宽并且适宜逐渐变窄到成为一个尖头的热传递翅片62。这些翅片62在敷设聚合物覆盖层以后应伸出到最终元件的内直径之外至少约0.125英寸,多到0.250英寸,以便将最大的热传导给流体如水。
键槽69的外部径向表面上最好具有能接纳较优电阻加热丝66的双螺旋线的对齐的槽。
虽然本发明热传递翅片62为支承骨架70的一部分,但这种翅片62也可成形为支承环60或在外面模塑的聚合物覆盖层64的一部分,或从多个这些表面上伸出。与此类似,热传递翅片62能被设置在键槽69的外侧,使它穿透到聚合物覆盖层64之外。另外,本发明设想可在所提供的加热元件的内表面或外表面上设置多个不规则的或几何形状的隆起或凹陷。已知这样一种热传递表面可使热量容易从表面上移走到液体内。它们可用多种方法设置,包括将它们注射模塑到聚合物覆盖层64或翅片62的表面内、蚀刻、喷砂或机械加工本发明的加热元件的外表面。
在本发明的较优实施例中,支承骨架70含有热塑性树脂,它可以是本文所说的“高温”聚合物中的一种,如对聚苯硫(PPS)加上少量的玻璃纤维作为结构支撑,并可任意选用陶瓷粉如Al2O3或MgO以便提高热传导率。或者支承骨架可以是一种熔融的陶瓷件,包括一种或多种的硅酸氧化铝、Al2O3、MgO、石墨、ZrO2、Si3N4、Y2O3、SiC、SiO2等,或者一个与所建议的“高温”聚合物不同的热塑性或热固性聚合物可被用于覆盖层30。如果热塑性塑料被用作支承骨架70,那么其热变形温度应大于用来模塑覆盖层30的熔化聚合物的温度。
支承骨架70被放置在绕线机上,所说较优的电阻加热丝66被叠合并环绕支承骨架70成双螺旋线的外形卷绕在较优的支承表面上即间隔开的槽66内。然后将完全卷绕好的支承骨架放置到注射模型内,用本发明的较优聚合物中的一种在外面进行包塑。在一较优的实施例中,只有一小部分热传递翅片62露出与流体接触,如果支承骨架为管状,那么支承骨架70的其余部分在内外两侧都被熔化的树脂覆盖。这个露出部分最好小于支承骨架70的表面面积的约10%。
构成支承骨架70的多个孔的开通的横截面面积使熔化的树脂更容易充填并在电阻加热丝66上作更大的覆盖,同时减少气泡和热点的发生。在较优的实施例中,孔面积应为支承骨架的整个管状表面面积的至少约10%,最好大于20%,使熔化的聚合物能更容易地环绕支承骨架70和电阻加热丝66流动。
图10-12示出另一种支承骨架200。该骨架也包括多条纵长的键槽260,其上设有间隔开的凹槽260用来接纳卷绕的电阻加热丝(未示出)。纵长键槽268最好用间隔开的支承环266夹持在一起。间隔开的支承环266具有“车轮”设计,其上设有多个辐条264和一个毂部262。这样可在支承骨架70上增加结构支承而不显著干扰较优的注射模型操作。
或者,本发明的聚合物覆盖层可用浸渍的方法来敷设,例如将外露的支承骨架70或200浸入到丸状化或粉状化的聚合物如PPS的流态化床内。在这样一个过程中,电阻丝应先卷绕到骨架的支承表面上并通上电流产生热量。如果采用PPS,那么在将支承骨架浸入到丸状化聚合物的流态化床内之前应产生至少约为500°F的温度。流态化床将使丸状化聚合物与加热的电阻丝紧密地接触,这样便可基本上均匀地提供一个聚合物覆盖层,该覆盖层可完全包围电阻加热丝并基本上包围支承骨架。这样造成的元件可包括一个比较结实的结构,具有相当多的开通的横截面面积,而电阻加热丝仍可气密地绝缘,不与流体接触。还应知道,支承骨架和电阻加热丝能被预热而不是将电流通到电阻加热丝内来产生足够的热量供熔化在其表面上的聚合物丸之用。这个过程还可包括流态化床以后的加热,以便得到更均匀的覆盖层。在目前的聚合物技术的技巧内还可对该过程作出其他修改。
本发明的较优的聚合物流体加热器的标准额定功率在加热水时为240V和4500W,虽然可以通过改变导电线圈14的长度和线的直径来提供从1000W到约6000W的多种功率,功率最好在约1700W到4500W之间。对于气体加热,可用较低的约为100-1200W的功率。两个甚至三个功率也可提供,只要将多个线圈或电阻材料终止在起作用的元件部10上的不同部位即可。
从上可知本发明能提供改进的流体加热元件供各种流体加热装置包括热水器和油空间加热器使用。本发明的较优装置主要是聚合物的,这样可减少费用,并可显著减少在流体存储箱内发生直流电流的作用。在本发明的某些实施例中,聚合物的流体加热器可与聚合物的存储箱结合使用,这样便可完全防止产生与金属离子有关的腐蚀。
或者,这些聚合物流体加热器可被这样设计使它们各有自己的存储容器,可分开来使用,同时存储并加热气体或液体。在这种实施例中,流动通过的空腔11可被模塑成箱或存储盆的形式,而加热线圈14可被包含在箱或盆的壁内,在通入电流时便可加热箱或盆内的液体或气体。本发明的加热装置还可用于食物温热器、卷发夹加热器、头发干燥器、烫发钳、衣服熨斗、及用于矿泉和泳池的休闲加热器。
本发明还可用于流动通过的加热器,其中流体介质流动通过含有本发明的一个或多个绕组或电阻材料的聚合物管。当流体介质通过这样一根管子的内直径时,电阻热便会产生,通过管子内直径的聚合物壁加热气体或液体。流动通过的加热器可用于头发干燥器和常被用来加热水的“按需”加热器中。
虽然上面示出了各种实施例,但只是为了说明的目的而不是要限制本发明。在所附权利要求限定的范围内,行家显然可以作出各种修改。
Claims (21)
1.一种电阻加热元件,能够通过一个箱壁设置,以便用来加热流体介质,该加热元件具有:
(a)一个第一突缘端(32);
(b)一个支承骨架(70),其一端上具有第一突缘端,并有一组穿过支承骨架的穿通孔,和在支承骨架上的第一支承表面;
(c)卷绕在所说第一支承表面(68)上并在所说加扭元件的所说第一突缘端连接到至少一对接线端端部的电阻丝(66);及
(d)一个设置在所说电阻丝外面的导热的聚合物覆盖层(64),用来气密地封装并使所说电阻丝与所说流体介质电绝缘。
2.按照权利要求1的加热元件,其特征为,所说支承骨架具有多条纵长键槽。
3.按照权利要求2的加热元件,其特征为,所说纵长键槽具有多条槽用来支承所说电阻丝。
4.按照权利要求3的加热元件,其特征为,还具有多个连接所说纵长键槽的支承环。
5.按照权利要求4的加热元件,其特征为,所说支承骨架还具有伸出到流体介质内的热传递翅片。
6.按照权利要求1的加热元件,其特征为,所说支承骨架为管状,所说孔具有所说管的整个表面面积的至少约10%,用来使在所说电阻丝外面的所说导热聚合物覆盖层容易模塑。
7.按照权利要求6的加热元件,其特征为,所说支承骨架具有多条纵长键槽,其上设有一连串的间隔开的槽用来接纳所说电阻丝。
8.按照权利要求7的加热元件,其特征为,所说支承骨架和所说导热聚合物覆盖层具有共同的热塑性树脂。
9.一种用来支承电阻加热元件的电阻丝的聚合物支承骨架具有:多条纵长键槽包括沿其长度间隔开的槽,多个从所说键槽伸出的热传递翅片,所说键槽由多个在纵向上间隔开的支承环连成整体。
10.一种热水器具有:
(a)一个容纳水的水箱;
(b)一个装到所说水箱壁的加热元件用来给所说水箱内的部分水电阻加热,所说加热元件具有:
一个支承骨架,其上设有多个穿通支承骨架的孔和一个在支承骨架上的第一支承表面;
卷绕在所说第一支承面并连接到至少一对接线端端部的电阻丝;及
一个设在所说电阻丝和大部分所说支承骨架外面的导热聚合物覆盖层用来气密地封装并使所说电阻丝与水电绝缘。
11.按照权利要求10的热水器,其特征为,所述支承骨架具有多条纵长键槽由多个支承环连成一个整体,这样形成一连串的侧壁孔,使在所说电阻丝外面的所说导热聚合物覆盖层容易模塑。
12.一种加热流体用的电阻元件的制造方法包括:
(a)提供一个支承骨架,其上具有多个穿通支承骨架的孔和一个在支承骨架上的支承表面;
(b)将电阻加热丝卷绕在所说支承表面上;
(c)将导热聚合物材料的覆盖层模塑在所说电阻加热丝和大部分所说支承骨架的外面以便气密地封装并使所说电阻加热丝与所说流体电绝缘。
13.按照权利要求12的方法,其特征为,所说支承骨架具有多条纵长键槽。
14.按照权利要求13的方法,其特征为,所说纵长键槽具有间隔开的槽用来支承所说电阻加热丝。
15.按照权利要求12的方法,其特征为,所说支承骨架和所说导热聚合物材料覆盖层具有共同的热塑性树脂。
16.按照权利要求12的方法,其特征为,所说工步(a)为注射模塑所说支承骨架,而所述工步(c)为注射模塑所说导热聚合物覆盖层以封装所说电阻加热丝和至少约90%的支承骨架。
17.按照权利要求16的方法,其特征为,所说支承骨架的其余10%包括多个热传递翅片。
18.一种电阻加热元件,它能通过水箱壁设置以便用来加热流体介质,该元件具有:
(a)一个聚合物支承骨架,其上设有多条纵长键槽被一连串的间隔开的支承环连接,所说纵长键槽具有间隔开的槽;
(b)具有一对自由端被连接到一对接线端端部上的电阻加热丝,所说电阻加热丝卷绕在所说间隔开的槽上并被该槽支承;及
(c)含有添加剂用来提高导热率的聚合物覆盖层设置在所说电阻丝和至少90%的所说支承骨架的外面,用来气密地封装并使所说电阻丝与所说流体电绝缘,其时所说支承骨架设有多个孔以便使所说聚合物覆盖物容易模塑。
19.按照权利要求18的加热元件,其特征为,所说支承骨架包括管状。
20.按照权利要求19的加热元件还具有设在所说管的内表面上的热传递翅片。
21.一种电阻加热元件,它能通过水箱壁设置,以便用来加热流体介质,该元件具有:
(a)一个管状聚合物的支承骨架,其上设有一个在支承骨架上的第一支承面;
(b)卷绕在所说第一支承面上并与至少一对接线端端部连接的电阻丝;
(c)一个设置在所说电阻丝和大部分所说支承骨架的外面的导热聚合物覆盖层,用来气密地封装并使所说电阻丝与所说流体介质电绝缘;及
(d)多个从所说加热元件的表面伸出的热传递翅片,用来对流体介质提供更有效的加热。
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US (2) | US5835679A (zh) |
EP (1) | EP0941632B1 (zh) |
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1996
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-
1997
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- 1997-11-20 TR TR1999/01168T patent/TR199901168T2/xx unknown
- 1997-11-20 JP JP52484598A patent/JP3832671B2/ja not_active Expired - Fee Related
- 1997-11-20 CA CA002265674A patent/CA2265674C/en not_active Expired - Fee Related
- 1997-11-20 BR BRPI9713543-7A patent/BR9713543B1/pt not_active IP Right Cessation
- 1997-11-20 ES ES97947631T patent/ES2259448T3/es not_active Expired - Lifetime
- 1997-11-20 WO PCT/US1997/021711 patent/WO1998024269A1/en active IP Right Grant
- 1997-11-20 PL PL97333823A patent/PL185058B1/pl not_active IP Right Cessation
- 1997-11-20 AU AU52671/98A patent/AU742484B2/en not_active Ceased
- 1997-11-20 DE DE69735381T patent/DE69735381T2/de not_active Expired - Lifetime
- 1997-11-20 CN CN97199214A patent/CN1128566C/zh not_active Expired - Fee Related
- 1997-11-20 HU HU9904511A patent/HU226288B1/hu not_active IP Right Cessation
- 1997-11-20 CZ CZ0182499A patent/CZ298182B6/cs not_active IP Right Cessation
- 1997-11-20 NZ NZ334555A patent/NZ334555A/xx not_active IP Right Cessation
- 1997-11-21 TW TW087100716A patent/TW382876B/zh not_active IP Right Cessation
- 1997-11-24 ID IDP973747A patent/ID18980A/id unknown
- 1997-11-25 MY MYPI97005655A patent/MY117015A/en unknown
- 1997-11-26 AR ARP970105546A patent/AR010308A1/es active IP Right Grant
-
1998
- 1998-11-04 US US09/186,017 patent/US6432344B1/en not_active Expired - Lifetime
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2000
- 2000-03-22 HK HK00101749A patent/HK1029483A1/xx not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
WO1998024269A1 (en) | 1998-06-04 |
BR9713543B1 (pt) | 2010-11-30 |
EP0941632A4 (en) | 2001-03-28 |
ES2259448T3 (es) | 2006-10-01 |
ID18980A (id) | 1998-05-28 |
DE69735381T2 (de) | 2006-10-19 |
HK1029483A1 (en) | 2001-03-30 |
CZ182499A3 (cs) | 1999-09-15 |
JP2001506796A (ja) | 2001-05-22 |
MY117015A (en) | 2004-04-30 |
CZ298182B6 (cs) | 2007-07-18 |
TW382876B (en) | 2000-02-21 |
CA2265674C (en) | 2004-09-14 |
HUP9904511A3 (en) | 2000-06-28 |
DE69735381D1 (de) | 2006-04-27 |
EP0941632A1 (en) | 1999-09-15 |
CA2265674A1 (en) | 1998-06-04 |
JP3832671B2 (ja) | 2006-10-11 |
AU742484B2 (en) | 2002-01-03 |
EP0941632B1 (en) | 2006-03-01 |
HU226288B1 (en) | 2008-07-28 |
NZ334555A (en) | 2001-01-26 |
US5835679A (en) | 1998-11-10 |
PL185058B1 (pl) | 2003-02-28 |
AU5267198A (en) | 1998-06-22 |
TR199901168T2 (xx) | 1999-07-21 |
HUP9904511A1 (hu) | 2000-05-28 |
BR9713543A (pt) | 2000-01-25 |
AR010308A1 (es) | 2000-06-07 |
CN1235748A (zh) | 1999-11-17 |
US6432344B1 (en) | 2002-08-13 |
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