CN1340111A - Method for machining a component surface - Google Patents
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- CN1340111A CN1340111A CN00803917A CN00803917A CN1340111A CN 1340111 A CN1340111 A CN 1340111A CN 00803917 A CN00803917 A CN 00803917A CN 00803917 A CN00803917 A CN 00803917A CN 1340111 A CN1340111 A CN 1340111A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/01—Selective coating, e.g. pattern coating, without pre-treatment of the material to be coated
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/18—After-treatment
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Abstract
本发明涉及一种用热喷涂产生的粒子束处理部件表面的方法。其中粒子束至少部分地按照一个预定的图样扫描要处理的部件表面。
This invention relates to a method for treating the surface of a component using a particle beam generated by thermal spraying. The particle beam scans the surface of the component to be treated, at least partially, according to a predetermined pattern.
Description
本发明涉及一种按照权利要求1的前序部分所述的利用等离子束对位于处理区域中的部件表面进行处理的方法。The invention relates to a method according to the preamble of claim 1 for the treatment of a surface of a component located in a treatment region with a plasma beam.
主要用于气缸曲轴箱的亚共晶铝硅合金由于耐磨的硅相成分太少而不适合用于活塞--活塞环--气缸工作面这个系统的摩擦负载。过共晶铝硅合金,例如合金AlSil7Cu4Mg具有足够的硅晶体成分。通过化学的和/或机械的处理步骤,相对于由铝晶体构成的母体,这种硬的耐磨的组织成分得到提高,并且构成一个必要的支承面成分。但是相对于亚共晶合金和准共晶合金,这种合金的缺陷是差的可铸性、差的可处理(可加工)性和高的成本。The hypoeutectic aluminum-silicon alloy, which is mainly used in the cylinder crankcase, is not suitable for the friction load of the piston-piston ring-cylinder working surface system because of too little silicon phase composition for wear resistance. Hypereutectic aluminum-silicon alloys, such as the alloy AlSil7Cu4Mg , have a sufficient silicon crystalline composition. Through chemical and/or mechanical treatment steps, this hard, wear-resistant structural component is increased relative to a matrix composed of aluminum crystals and forms an essential support surface component. However, disadvantages of such alloys are poor castability, poor handleability (machinability) and high cost relative to hypoeutectic and quasi-eutectic alloys.
克服这些缺陷的一个可能性是铸入由耐磨材料,例如灰铸铁合金和过晶体铝合金制成的气缸套。但是此时的问题是缸套和重铸材料之间的结合,这只是通过机械的咬合来保证的。通过采用一种多孔的陶瓷缸套材料,可以在浇铸过程中使该陶瓷缸套材料浸入而形成一种材料间的结合。此时要求对模子进行缓慢的充填和应用高的压力,这使该方法的经济性大大降低。One possibility to overcome these disadvantages is to cast in cylinder liners made of wear-resistant materials such as gray cast iron alloys and supercrystalline aluminum alloys. But the problem at this time is the bond between the cylinder liner and the recast material, which is only guaranteed by mechanical engagement. By using a porous ceramic liner material, it is possible to impregnate the ceramic liner material during the casting process to form a material-to-material bond. This requires slow filling of the mold and application of high pressure, which greatly reduces the economics of the method.
另一种方法是将亚共晶合金和准共晶合金作为电镀涂层直接涂覆到工作面上。但是这种方法很昂贵并且从摩擦化学上来说其耐磨性不够。还有一种方法是构成热喷涂层,它们同样也是直接施加到工作面上的。但是,由于仅仅是微力学上的连接,这些涂层的粘合强度是不够的。Another method is to apply hypoeutectic alloys and quasi-eutectic alloys directly to the working surface as electroplated coatings. However, this method is expensive and is not sufficiently wear-resistant tribochemically. Yet another method is to form thermal spray coatings, which are likewise applied directly to the work surface. However, the adhesive strength of these coatings is insufficient due to the mere micromechanical connection.
因此已经有人建议使用激光器对表面进行再熔化、注入合金材料、弥散处理和涂覆涂层,对表面实施改良,例如由文献DE19643029A1中公开的那样。但是此时的缺陷是,这样制成的气缸工作面涂面具有太多的孔眼,并且其浸入深度较小,结果,涂覆的涂层的粘附力较小,不符合要求。It has therefore already been proposed to modify the surface by remelting it with a laser, injecting an alloy material, dispersing it and applying a coating, as disclosed, for example, in document DE 196 43 029 A1. The disadvantage here, however, is that the cylinder face coating produced in this way has too many perforations, and its immersion depth is low, as a result, the adhesion of the applied coating is low, which is not satisfactory.
本发明的任务是,提供一种改进的上述种类的方法,它们克服了前面所提到的缺陷并能在短的处理时间内实现快速生产。The object of the present invention is to provide an improved method of the above-mentioned kind which overcomes the disadvantages mentioned above and which enables rapid production with short processing times.
按照本发明,这个任务是通过一个具有权利要求1中的特征部分的特征的上述种类的方法解决的。在从属权利要求中给出了本发明的一些有利的方案。According to the invention, this object is solved by a method of the above-mentioned kind with the characterizing features of claim 1 . Some advantageous developments of the invention are given in the dependent claims.
按照本发明,在一个上述种类的方法中,规定粒子束至少部分地按照一个预定的图样扫描要处理的部件表面。According to the invention, in a method of the above-mentioned kind it is provided that the particle beam scans the surface of the component to be treated at least partially according to a predetermined pattern.
它的优点在于,通过对例如较小负荷区域只进行部分的处理,达到缩短处理时间的目的。This has the advantage that a reduction in processing time is achieved by only partially processing, for example, less loaded areas.
合适的方式是借助于火焰喷涂、带有等离子束的等离子喷涂或高压喷涂实施热喷涂。A suitable way is to carry out thermal spraying by means of flame spraying, plasma spraying with a plasma beam or high-pressure spraying.
例如预定的图样至少包括对要处理的表面有一次扫描、尤其是两次反向的扫描或者以一个预定的上升角α例如1°-90°多次螺旋形的扫描。该图样的另一种情况或者附加地包括一个对要处理的表面进行的线形的、角形的、交叉状或点状的扫描。当此时要处理的表面是内燃机曲轴箱的一个气缸中与活塞相配合的气缸工作面时,那么按照目的的要求,按照一个预定图样的扫描是在活塞的上死点和下死点之间的一个区域中进行的。For example, the predetermined pattern includes at least one scan of the surface to be treated, especially two reverse scans or multiple helical scans at a predetermined ramp angle α, for example 1°-90°. Alternatively or additionally, the pattern can include a linear, angular, cross-shaped or point-shaped scan of the surface to be treated. When the surface to be processed at this time is the cylinder working surface that matches the piston in a cylinder of the internal combustion engine crankcase, then according to the requirements of the purpose, the scanning according to a predetermined pattern is between the top dead center and the bottom dead center of the piston. carried out in an area of .
在部件的例如承受高负荷的区域中,等离子束对要处理的部件表面的扫描至少部分是全表面的,以便在全表面上实现合金化。如果此时要加工的表面是内燃机曲轴箱的一个气缸中与活塞相配合的气缸工作面,那么,全表面的扫描最好在活塞的上死点和下死点之间的一个区域中进行。此时全表面的扫描例如至少在一个高度上进行,该高度相应于活塞的活塞环组的宽度,其中尤其有利的是全表面扫描要超过活塞的活塞环组的宽度的量为活塞行程的12%,例如大约为5mm。In regions of the component that are exposed to high loads, for example, the plasma beam scans the surface of the component to be treated at least partially over the entire surface in order to achieve alloying over the entire surface. If the surface to be machined is the cylinder running surface associated with the piston in a cylinder of the crankcase of the internal combustion engine, then the scanning of the entire surface is preferably carried out in an area between the upper dead center and the lower dead center of the piston. In this case, the scanning of the full surface is carried out, for example, at least at a height corresponding to the width of the piston ring set of the piston, wherein it is particularly advantageous that the full surface scan will exceed the width of the piston ring set of the piston by 12 times the piston stroke. %, for example about 5mm.
通过在紧靠近粒子束接触区之前的局部区域、在该区域中和/或在该区域之后的局部区域中,用激光束对部件的材料实施熔化,而获得一种处理结果,即浸入深度更大,材料进入更好以及用等离子束涂覆的材料与部件的材料的连接更好。By melting the material of the component with the laser beam in a local area immediately before, in this area and/or in a local area after this area of contact with the particle beam, a process result is obtained in which the immersion depth is lower. Larger, better material entry and better bonding of the material coated with the plasma beam to the material of the component.
为了进一步改善涂覆的材料层的性能,在处理后对部件表面附加地用激光束处理,尤其是再熔化。In order to further improve the properties of the applied material layer, the component surface is additionally treated with a laser beam after treatment, in particular remelted.
依照目的的要求,通过熔化涂覆区中的部件材料而构成一个熔池。According to the requirements of the purpose, a molten pool is formed by melting the component material in the coating zone.
例如,部件是用铝制造的,并且尤其是一个活塞式内燃机的曲轴箱,在它的气缸的气缸工作面上要进行涂层处理。此时在一个优选的实施例中,在制造耐磨的表面期间,在曲轴箱的水腔中通流一种冷却介质,尤其是气体氮或者一种冷却液体。For example, components are made of aluminum and in particular the crankcase of a piston internal combustion engine is coated on the cylinder running surfaces of its cylinders. In a preferred embodiment, a cooling medium, in particular gaseous nitrogen or a cooling liquid, flows through the water chamber of the crankcase during production of the wear-resistant surface.
为了制造一个耐磨表面,以尤其有利的方式,借助于粒子束将一种粉态材料,尤其是硅或一种硅合金涂布在部件的材料上,此时该部件的材料最好是铝。In order to produce a wear-resistant surface, in a particularly advantageous manner, a powdery material, especially silicon or a silicon alloy, is applied by means of a particle beam to the material of the component, which is preferably aluminum at this time .
例如通过表面处理,在部件的表面上构成一个耐磨表面,尤其是热喷涂层形式的耐磨表面。此时尤其有利的是,在制造耐磨表面的处理过程中,接着实施一个珩磨工序作为补充处理,由此可以磨平硬化的表面。A wear-resistant surface, in particular in the form of a thermally sprayed layer, is formed on the surface of the component, for example by surface treatment. It is particularly advantageous in this case if, during the process for producing the wear-resistant surface, a subsequent honing process is carried out as a supplementary process, whereby the hardened surface can be smoothed.
从从属权利要求以及下面对照附图对本发明进行说明中可以得出本发明的其它特征、优点和有利的结构。附图中,Additional features, advantages and advantageous configurations of the invention emerge from the subclaims and from the following description of the invention with reference to the figures. In the attached picture,
图1是一个用一个等离子束和一个激光束处理部件表面的装置的示意截面图,Figure 1 is a schematic cross-sectional view of an apparatus for treating the surface of a component with a plasma beam and a laser beam,
图2是一个处理区的一个放大的视图,Figure 2 is an enlarged view of a treatment area,
图3是一个按照本发明的处理图样的第一优选实施例的示意图,Figure 3 is a schematic diagram of a first preferred embodiment of a processing pattern according to the present invention,
图4是一个按照本发明的处理图样的第二优选实施例的示意图,Figure 4 is a schematic diagram of a second preferred embodiment of a processing pattern according to the present invention,
图5是一个按照本发明的处理图样的另一个优选实施例的示意图。Fig. 5 is a schematic diagram of another preferred embodiment of a processing pattern according to the present invention.
在图1和2示出的用于表面处理的装置的一个优选实施例包括一个等离子燃烧器10和一个激光器12,其中等离子燃烧器10发出带有一种涂层材料16的等离子束14,激光器12发出激光束18。一个要处理的部件在此处是一个未详细示出的具有相应的气缸孔19的曲轴箱,其中要处理的是气缸壁22的表面20。曲轴箱例如是用铝制造的,对表面20的处理是为了在气缸的工作面的区域中构成一个耐磨表面,在这个工作面上一个没有示出的活塞在气缸19中上下运动。为此涂层材料16例如是粉态的硅,它作为被熔化的涂层元件通过等离子束14涂覆到表面20上。为此将等离子燃烧器10伸入到气缸19中并围绕自身轴线转动,如箭头24(见图1)和25(见图2)所示,使等离子束14扫描表面20。等离子束14现时接触的那个区域以下称为处理区或涂层区26。在该区域中涂层材料16进入到气缸壁22的材料中。A preferred embodiment of the device for surface treatment shown in FIGS. 1 and 2 comprises a
在等离子燃烧器10之外附加设置的激光器12是这样布置的,即沿处理方向25激光器12在等离子燃烧器10之前接触表面20。此时是这样选择激光器12的能量的,在激光束18的接触点上气缸壁22的材料被熔化,从而在等离子束14接触之前形成一个熔化区或熔池28。换言之,等离子束14紧跟随激光束18,将等离子体中含有的涂层材料16加入熔化区28中。这样涂层材料16以最佳的方式被合金结合到气缸壁22的材料中。The
由此一种激光涂覆和一种等离子涂覆相结合并在一个单独的工序中实施。此时激光束18和等离子束14之间的间距是激光功率、所希望的熔化深度、熔化区长度、气缸壁22的材料的反射率和气缸19的直径等因素的函数。A laser coating and a plasma coating are thus combined and carried out in a single process. The distance between the
此时按照本发明,由激光束18和等离子束14构成的双束对表面20的扫描不是在整个气缸工作面上全表面地进行的,而是在预定的区域按照预定的图样进行的。图3至5示出了这种图样的例子,作为激光注入合金和涂覆的通道29。Now according to the present invention, the scanning of the
如从图3中可见,在一个未示出的活塞的上死点30(OT)和下死点32(UT)的区域中的扫描是在全表面上进行的,并且扫描的高度相应于活塞环组的高度34加上例如5毫米,相当于活塞行程的12%。在OT30和UT32之间的区域中对表面20的扫描是在一个1至90度的上升角@下螺旋地进行的。As can be seen from FIG. 3, the scanning in the region of the upper dead center 30 (OT) and the lower dead center 32 (UT) of a piston, not shown, is carried out over the full surface, and the height of the scanning corresponds to the height of the piston The
在图4的图样中,是沿着两条相对的螺旋线对表面20扫描的。此时在一个没有示出的优选结构中,还采用三条或多条螺旋线。按照图5的实施例,对表面20的扫描是线形地、角形地、交叉地或点状地进行的。In the pattern of Figure 4, the
在承受较小负荷区域中对表面20只进行部分扫描,一方面保证气缸工作面具有足够的耐磨表面,另一方面缩短了制造中的处理时间,相应地降低了费用。Partial scanning of the
按照本发明,利用激光器12是为了提高亚共晶铝合金和准共晶铝合金的边缘层着的硅成分16。为此在一个所示的单步骤的方法中,在用激光处理期间,以合适的供入量将铝硅粉施加到产生的熔化区28中。根据负荷的情况此时可以实现2毫米以上的涂层厚度。此时与基础材料的混合程度的要求很小。在供入的粉中的硅成分含量在20%和40%之间的范围中。如果要求具有高混合程度的极小的涂层厚度,则将采用硅成分含量在40%和60%之间的粉16。由于粉粒16应该在熔化区28中完全溶解,因此所选择的加工参数如前移速度和激光功率必须保证有一个最小的熔池寿命。选择一个合适的束强度分布有利于降低处理的费用。此外,具有尽可能直角横截面的熔核以及由此产生很少的线路交叉重叠点是有利的。In accordance with the present invention, the
除了根据需要对整个气缸工作面进行全表面的合金处理之外,主要是进行部分的处理。在活塞上下转向点处(上死点30和下死点32)的高负荷区域是全表面再熔化的,而在其之间的低负荷区域只设置了个别的激光处理线路(例如菱形图样,参见图3至5),它在此处提供了足够的摩擦保护。这种做法大大地缩短了加工时间,因为只需要处理很小部分的工作面表面。如果整个工作面表面或大部分都需要进行激光表面处理,那么就需要对曲轴箱进行冷却,例如这可以通过使一种冷却介质流过曲轴箱的现存的冷却水系统来实现。在只进行部分处理时,除了从上下侧除去带入的能量外,例如通过与水冷却的铜板接触来除去该能量就足够了。In addition to the alloy treatment of the entire cylinder working surface as required, the treatment is mainly partial. The high load areas at the upper and lower turning points of the piston (top
总之,本发明提出了一种热喷涂(等离子喷涂)和激光表面处理的组合。此时,通过再熔化先前涂覆的喷涂层,避免了涂层的多孔性,并且在足够大的熔化深度下与基础金属产生了连接。合适的是只在高负荷区域用激光器12进行全表面的再熔化,而在其余区域不做再熔化或者只在一个图样型例如菱形、阴影部分和点状图样的区域中进行再熔化。In conclusion, the present invention proposes a combination of thermal spraying (plasma spraying) and laser surface treatment. In this case, by remelting the previously applied spray layer, the porosity of the coating is avoided and a connection with the base metal is produced at a sufficiently large melting depth. It is suitable to carry out full-surface remelting with
不是仅仅存在这样的可能性,即对已涂覆的喷涂层进行补充性的再熔化处理。在沿着前移方向25直接位于等离子涂覆区的前面,由激光束12产生的熔池28导致以固态或液态供入的粉粒16与基层产生金属性连接。在高的前移速度下,涂层结构是由基层材料、具有溶解的和仅仅部分地熔化的原粉粒16的薄的合金区以及一个相对较厚的喷涂层构成的。由于在相应选择的加工参数下使微咬合得到改善,通过该中间涂层可以使喷涂层和合金层之间的涂层粘附力大大提高,这就省去了以前为了使喷涂层达到足够的涂层粘附力而对要涂覆的涂层表面20必须做昂贵的、高成本的预处理(清洗和照射)。此时可以在所述的用于部件表面处理的涂覆处理之后再结合一个磨光表面的珩磨处理。It is not the only possibility to carry out a supplementary remelting treatment of the applied spray coating. Immediately in front of the plasma-coating zone along the advancing
对优选实施例的上述说明应理解为只是用例子解释本发明。本发明的一个可变通的和特别优选的实施例在于,将热喷涂和激光表面处理这样地结合起来,使得在用热喷涂在全表面上涂覆涂层材料16时或者在全表面上喷涂气缸的工作面时,激光器或激光束只照射局部线路部分,其中的线路的构成类似于前面针对等离子涂覆所说明的图样。此时,激光器例如在喷涂处理时是持续地一起移动的,但只是部分地接通,从而获得一个要求的图样。The above description of the preferred embodiment is to be understood as illustrating the invention by way of example only. A flexible and particularly preferred embodiment of the invention consists in combining thermal spraying and laser surface treatment in such a way that when the
Claims (19)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19907102 | 1999-02-19 | ||
| DE19907102.0 | 1999-02-19 | ||
| DE19941564A DE19941564A1 (en) | 1999-02-19 | 1999-09-01 | Process for processing a surface of a component |
| DE19941564.1 | 1999-09-01 |
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| Publication Number | Publication Date |
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| CN1340111A true CN1340111A (en) | 2002-03-13 |
| CN1192123C CN1192123C (en) | 2005-03-09 |
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| CNB008039178A Expired - Fee Related CN1192123C (en) | 1999-02-19 | 2000-01-26 | Methods of Treating Part Surfaces |
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| EP (1) | EP1161571B1 (en) |
| CN (1) | CN1192123C (en) |
| WO (1) | WO2000049195A1 (en) |
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| CN104031280A (en) * | 2014-06-16 | 2014-09-10 | 滁州市宏源喷涂有限公司 | Treatment process for hardening plastic surface |
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| US7458358B2 (en) * | 2006-05-10 | 2008-12-02 | Federal Mogul World Wide, Inc. | Thermal oxidation protective surface for steel pistons |
| CN104419883A (en) * | 2013-09-09 | 2015-03-18 | 北京赛亿科技股份有限公司 | Method for intensifying plasma beam on surface of combustion chamber of aluminum piston of internal combustion engine |
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| DD242638A1 (en) * | 1985-11-18 | 1987-02-04 | Ibr Fuer Entwickl Techn U Rat | METHOD FOR IMPROVING ADHESIVE STRENGTH OF METAL INJECTION LAYERS |
| US4897283A (en) * | 1985-12-20 | 1990-01-30 | The Charles Stark Draper Laboratory, Inc. | Process of producing aligned permanent magnets |
| US5079043A (en) * | 1990-12-03 | 1992-01-07 | The Perkin-Elmer Corporation | Method for spraying a coating on a disk |
| US5271967A (en) * | 1992-08-21 | 1993-12-21 | General Motors Corporation | Method and apparatus for application of thermal spray coatings to engine blocks |
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| CN104031280A (en) * | 2014-06-16 | 2014-09-10 | 滁州市宏源喷涂有限公司 | Treatment process for hardening plastic surface |
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| WO2000049195A1 (en) | 2000-08-24 |
| EP1161571B1 (en) | 2004-06-16 |
| CN1192123C (en) | 2005-03-09 |
| EP1161571A1 (en) | 2001-12-12 |
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