TW201606133A - Cermet coating - Google Patents
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- TW201606133A TW201606133A TW103127605A TW103127605A TW201606133A TW 201606133 A TW201606133 A TW 201606133A TW 103127605 A TW103127605 A TW 103127605A TW 103127605 A TW103127605 A TW 103127605A TW 201606133 A TW201606133 A TW 201606133A
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本發明是有關於一種瓷金(cermet)塗層，特別是指一種由一瓷金粉末經由高速火焰熔射形成的瓷金塗層。 This invention relates to a cermet coating, and more particularly to a porcelain gold coating formed by a high velocity flame spray of a porcelain gold powder.
為了使熱浸鍍鋅產線之熱浸鍍鋅槽內所使用的輥輪具有耐磨、耐高溫氧化以及耐熔融鋅腐蝕的效果，輥輪的表面為以瓷金粉末經由高速火焰熔射法所形成的瓷金塗層，且輥輪的表面需具有100μm以上的厚度。其中，因為在製備輥輪過程中，輥輪還需先經過例如噴砂、研磨、挖溝槽等加工處理才能於熱浸鍍鋅產線上使用，因此由瓷金粉末形成的瓷金塗層一開始需先具有至少150μm的厚度才能因應在加工處理中的損耗。 In order to make the roller used in the hot dip galvanizing tank of the hot dip galvanizing line have the effects of wear resistance, high temperature oxidation resistance and resistance to molten zinc corrosion, the surface of the roller is made of porcelain gold powder by high speed flame spraying method. The porcelain gold coating is formed, and the surface of the roller needs to have a thickness of 100 μm or more. Among them, because in the process of preparing the roller, the roller needs to be processed by hot-dip galvanizing line through processing such as sand blasting, grinding, trenching, etc., so the porcelain gold coating formed by the porcelain gold powder begins. It is necessary to have a thickness of at least 150 μm in order to cope with the loss in the processing.
然而，針對使瓷金塗層具有至少150μm的厚度的目的，目前業界仍亟需設法就瓷金粉末的組成及性質進行調整，並配合高速火焰熔射方法進行改善。 However, for the purpose of making the porcelain gold coating have a thickness of at least 150 μm, there is still an urgent need in the industry to adjust the composition and properties of the porcelain gold powder, and to improve it by the high-speed flame spraying method.
因此，本發明之目的，即在提供一種瓷金塗層，該瓷金塗層具有150μm以上的厚度。 Accordingly, it is an object of the present invention to provide a porcelain gold coating having a thickness of 150 μm or more.
於是本發明瓷金塗層，是由一瓷金粉末經高速 火焰熔射所形成，其中，該瓷金粉末包含複數個瓷金顆粒，每一瓷金顆粒含有碳化鎢、碳化硼、鈷、鉻及鈷-鉻合金，且在每一瓷金顆粒中，鈷-鉻合金的表面積與該瓷金顆粒的表面積的比值為20%至40%，以及每一瓷金顆粒的粒徑範圍為20μm至53μm。 Therefore, the porcelain gold coating of the present invention is made of a porcelain gold powder through a high speed. Formed by flame spraying, wherein the porcelain gold powder comprises a plurality of porcelain gold particles, each of the porcelain gold particles containing tungsten carbide, boron carbide, cobalt, chromium and cobalt-chromium alloy, and in each porcelain gold particle, cobalt The ratio of the surface area of the chromium alloy to the surface area of the porcelain gold particles is 20% to 40%, and the particle size of each porcelain gold particle ranges from 20 μm to 53 μm.
本發明之功效在於：藉由該每一瓷金顆粒中鈷-鉻合金的表面積與該瓷金顆粒的表面積的比值為20%至40%，以及每一瓷金顆粒的粒徑範圍為20μm至53μm的瓷金粉末，並配合高速火焰熔射，能使得所形成的瓷金塗層具有150μm以上的厚度。 The effect of the invention is that the ratio of the surface area of the cobalt-chromium alloy in each of the porcelain gold particles to the surface area of the porcelain gold particles is 20% to 40%, and the particle size of each porcelain gold particle ranges from 20 μm to The 53 μm porcelain gold powder, combined with high-speed flame spraying, enables the formed porcelain gold coating to have a thickness of 150 μm or more.
以下將就本發明內容進行詳細說明：該瓷金粉末是由一包括複數個碳化鎢顆粒、複數個碳化硼顆粒、複數個鈷顆粒及複數個鉻顆粒的混合物經粒化燒結法(granulation sintering method)所製得。 The invention will be described in detail below: the porcelain gold powder is subjected to a granulation sintering method by a mixture comprising a plurality of tungsten carbide particles, a plurality of boron carbide particles, a plurality of cobalt particles and a plurality of chromium particles. ) made.
以費氏法(Fisher method)量測得到的碳化鎢顆粒的平均粒徑範圍為1.5μm至2.5μm，硼化鎢顆粒的平均粒徑範圍為4.5μm至6μm，鈷顆粒的平均粒徑範圍為1μm至3μm，鉻顆粒的平均粒徑範圍為7μm至8μm。以雷射粒徑分析法量測得到的碳化鎢顆粒的平均粒徑範圍為5μm至7μm，硼化鎢顆粒的平均粒徑範圍為10μm至12μm，鈷顆粒的平均粒徑範圍為7.5μm至小於8μm，鉻顆粒的平均粒徑範圍為7.8μm至小於10μm。混合物中的碳化鎢顆粒、硼化鎢顆粒、鈷顆粒及鉻顆粒的平均粒徑在上述範圍，顆粒混合的均勻性較佳，且燒結時的反應活性較 佳。 The average particle diameter of the tungsten carbide particles measured by the Fisher method is in the range of 1.5 μm to 2.5 μm, the average particle diameter of the tungsten boride particles is in the range of 4.5 μm to 6 μm, and the average particle diameter range of the cobalt particles is From 1 μm to 3 μm, the chromium particles have an average particle diameter ranging from 7 μm to 8 μm. The tungsten carbide particles measured by the laser particle size analysis method have an average particle diameter ranging from 5 μm to 7 μm, the tungsten boride particles have an average particle diameter ranging from 10 μm to 12 μm, and the cobalt particles have an average particle diameter ranging from 7.5 μm to less. The average particle size of the chromium particles of 8 μm ranges from 7.8 μm to less than 10 μm. The average particle diameter of the tungsten carbide particles, the tungsten boride particles, the cobalt particles and the chromium particles in the mixture is in the above range, the uniformity of particle mixing is better, and the reactivity at the time of sintering is higher. good.
該混合物還包含一分散劑及一粘結劑。 The mixture also contains a dispersing agent and a binder.
該分散劑例如但不限於：酒精或水等。例如當該分散劑為水時，碳化鎢顆粒、碳化硼顆粒、鈷顆粒及鉻顆粒的總重對水的重量的比例為55：45至75：25，碳化鎢顆粒、碳化硼顆粒、鈷顆粒及鉻顆粒的總重過多，則使瓷金粉末中的每一瓷金顆粒的粒徑過大；碳化鎢顆粒、碳化硼顆粒、鈷顆粒及鉻顆粒的總重過少，則使瓷金粉末中的每一瓷金顆粒的鬆裝密度太低。較佳地，碳化鎢顆粒、碳化硼顆粒、鈷顆粒及鉻顆粒的總重對水的重量的比例為60：40至70：30。 The dispersing agent is, for example but not limited to, alcohol or water. For example, when the dispersant is water, the ratio of the total weight of the tungsten carbide particles, the boron carbide particles, the cobalt particles and the chromium particles to the weight of water is 55:45 to 75:25, tungsten carbide particles, boron carbide particles, cobalt particles And the total weight of the chromium particles is too large, so that the particle size of each porcelain gold particle in the porcelain gold powder is too large; the total weight of the tungsten carbide particles, the boron carbide particles, the cobalt particles and the chromium particles is too small, so that the porcelain gold powder is The bulk density of each porcelain gold particle is too low. Preferably, the ratio of the total weight of the tungsten carbide particles, the boron carbide particles, the cobalt particles and the chromium particles to the weight of water is from 60:40 to 70:30.
該粘結劑例如但不限於：石蠟(paraffin)、蜂蠟(beeswax)或聚乙烯醇(PVA)等。更具體地說，當該分散劑為水時，配合該分散劑而使用的黏結劑為聚乙烯醇。且以該混合物的總量為100wt%，聚乙烯醇的含量範圍為0.5至5wt%，該聚乙烯醇的含量小於0.5wt%時，各顆粒間的黏結不佳，在燒結前及燒結後容易破裂；該聚乙烯醇的含量大於5wt%時，每一瓷金顆粒的粒徑過大且鬆裝密度低；較佳地，聚乙烯醇的含量範圍為1.5至2.5wt%。當該分散劑為酒精時，配合該分散劑而使用的黏結劑為石蠟或蜂蠟。 The binder is, for example but not limited to, paraffin, beeswax or polyvinyl alcohol (PVA). More specifically, when the dispersing agent is water, the binder used in combination with the dispersing agent is polyvinyl alcohol. And the total amount of the mixture is 100% by weight, the content of polyvinyl alcohol is in the range of 0.5 to 5% by weight, and when the content of the polyvinyl alcohol is less than 0.5% by weight, the adhesion between the particles is poor, and it is easy to be before and after sintering. When the content of the polyvinyl alcohol is more than 5% by weight, the particle diameter of each of the porcelain gold particles is too large and the bulk density is low; preferably, the content of the polyvinyl alcohol is in the range of 1.5 to 2.5% by weight. When the dispersing agent is alcohol, the binder used in combination with the dispersing agent is paraffin wax or beeswax.
該混合物的製備方式例如為：將碳化鎢顆粒、硼化鎢顆粒、鈷顆粒、鉻顆粒及分散劑混合後，以攪拌研磨機研磨30分鐘至60分鐘，即製得該混合物。其中，研磨時間低於30分鐘，則該等顆粒在分散劑中分散不佳，且 無法打散具有團聚的混合物；研磨時間大於60分鐘，則研磨機中的鉻鋼研磨球的鐵會釋出至混合物中，從而使後續製得的瓷金塗層具有鐵而增加瓷金塗層與鋅反應的腐蝕途徑。該粒化燒結法包含以下步驟：(1).提供一包含複數個碳化鎢顆粒、複數個硼化鎢顆粒、複數個鈷顆粒、複數個鉻顆粒、分散劑及粘結劑的混合物；(2).將該混合物進行噴霧乾燥處理(spray dry)，粒化(granulate)該混合物，形成粉末；(3).篩分(sieve)該粉末，以選出顆粒粒徑範圍為25μm至63μm的粉末，再將該顆粒粒徑範圍25μm至63μm的粉末在真空或還原氣氛中以1300至1450℃進行燒結(sinter)，燒結時間為1至4小時，形成一粉末團塊；(4).壓碎(crush)解離該粉末團塊，使燒結後稍微結合的顆粒分離，並篩分出適當粒徑範圍的粉末，即得到本發明所使用的瓷金粉末。 The mixture is prepared, for example, by mixing tungsten carbide particles, tungsten boride particles, cobalt particles, chromium particles, and a dispersing agent, and grinding the mixture in a stirring mill for 30 minutes to 60 minutes to prepare the mixture. Wherein, if the grinding time is less than 30 minutes, the particles are poorly dispersed in the dispersing agent, and Unable to break up the agglomerated mixture; if the grinding time is more than 60 minutes, the iron of the chrome steel grinding ball in the grinder will be released into the mixture, so that the subsequently produced porcelain gold coating has iron and increases the porcelain gold coating. Corrosion pathway that reacts with zinc. The granulation sintering method comprises the following steps: (1) providing a mixture comprising a plurality of tungsten carbide particles, a plurality of tungsten boride particles, a plurality of cobalt particles, a plurality of chromium particles, a dispersing agent and a binder; The mixture is subjected to spray drying, granulates the mixture to form a powder, and (3) sieves the powder to select a powder having a particle size ranging from 25 μm to 63 μm. The powder having a particle size ranging from 25 μm to 63 μm is further sintered at 1300 to 1450 ° C in a vacuum or reducing atmosphere for a sintering time of 1 to 4 hours to form a powder agglomerate; (4) crushing ( Crush) dissociates the powder agglomerates, separates the slightly bound particles after sintering, and sieves out the powder of the appropriate particle size range to obtain the porcelain gold powder used in the present invention.
更詳細地說，為得到每一瓷金顆粒中的鈷-鉻合金的表面積與該瓷金顆粒的表面積的比值為20%至40%，以及每一瓷金顆粒的粒徑範圍為20μm至53μm的瓷金粉末，所以在該步驟(3)中，於燒結前要篩分選出顆粒粒徑範圍為25μm至63μm的粉末，並配合燒結溫度為1300至1450℃以及燒結時間為1至4小時。若燒結前粉末的顆粒粒徑小於25μm，則顆粒容易相黏，從而使粉末團塊中稍微結合的顆粒不易在步驟(4)的壓碎過程中分離成單一的顆 粒；且若燒結前粉末的顆粒粒徑小於25μm，也會使鈷及鉻的含量不足，從而使得鈷-鉻合金的表面積與該瓷金顆粒的表面積的比值會小於20%。燒結溫度小於1300℃，則鈷-鉻合金的表面積與該瓷金顆粒的表面積的比值會小於20%。燒結溫度大於1450℃，且燒結時間大於4小時，則所形成的粉末團塊中合金互溶的程度較大，會使顆粒間的黏結過強，從而使壓碎時顆粒不易分離。較佳地，在該步驟(3)中，篩分選出顆粒粒徑範圍為25μm至63μm的粉末，燒結溫度為1375至1450℃，燒結時間為2至3小時。 In more detail, the ratio of the surface area of the cobalt-chromium alloy in each of the porcelain gold particles to the surface area of the porcelain gold particles is 20% to 40%, and the particle size of each porcelain gold particle ranges from 20 μm to 53 μm. The porcelain gold powder, so in this step (3), the powder having a particle size ranging from 25 μm to 63 μm is sieved before sintering, and the sintering temperature is 1300 to 1450 ° C and the sintering time is 1 to 4 hours. If the particle size of the powder before sintering is less than 25 μm, the particles are easily viscous, so that the slightly bonded particles in the powder agglomerate are not easily separated into a single particle during the crushing process of the step (4). If the particle size of the powder before sintering is less than 25 μm, the content of cobalt and chromium may be insufficient, so that the ratio of the surface area of the cobalt-chromium alloy to the surface area of the porcelain gold particles is less than 20%. When the sintering temperature is less than 1300 ° C, the ratio of the surface area of the cobalt-chromium alloy to the surface area of the porcelain gold particles may be less than 20%. When the sintering temperature is greater than 1450 ° C and the sintering time is more than 4 hours, the degree of mutual solubility of the alloy in the formed powder agglomerates is large, and the adhesion between the particles is too strong, so that the particles are not easily separated during crushing. Preferably, in this step (3), the powder having a particle size ranging from 25 μm to 63 μm is selected by sieving, the sintering temperature is from 1375 to 1450 ° C, and the sintering time is from 2 to 3 hours.
較佳地，每一瓷金顆粒的鬆裝密度為3.3g/cm3至3.9g/cm3。若每一瓷金顆粒的鬆裝密度小於3.3g/cm3，則由瓷金粉末所形成的瓷金塗層的孔洞過多。若每一瓷金顆粒的鬆裝密度大於3.9g/cm3，則熔射的火燄溫度無法熔融瓷金顆粒。 Preferably, each porcelain gold particle has a bulk density of from 3.3 g/cm 3 to 3.9 g/cm 3 . If the bulk density of each of the porcelain gold particles is less than 3.3 g/cm 3 , the pores of the porcelain gold coating formed of the porcelain gold powder are excessive. If the bulk density of each porcelain gold particle is more than 3.9 g/cm 3 , the flame temperature of the spray cannot melt the porcelain gold particles.
較佳地，在每一瓷金顆粒中，鈷-鉻合金的表面積與該瓷金顆粒的表面積的比值為30%至40%。更佳地，在每一瓷金顆粒中，鈷-鉻合金的表面積與該瓷金顆粒的表面積的比值為35%至40%。 Preferably, in each of the porcelain gold particles, the ratio of the surface area of the cobalt-chromium alloy to the surface area of the porcelain gold particles is 30% to 40%. More preferably, in each of the porcelain gold particles, the ratio of the surface area of the cobalt-chromium alloy to the surface area of the porcelain gold particles is from 35% to 40%.
較佳地，以每一瓷金顆粒的總重為100wt%，碳化鎢的含量範圍為60至63wt%。當碳化鎢的含量範圍為60至63wt%時，由瓷金粉末所形成的瓷金塗層的硬度較佳。 Preferably, the total weight of each porcelain gold particle is 100% by weight, and the content of tungsten carbide ranges from 60 to 63% by weight. When the content of tungsten carbide is in the range of 60 to 63% by weight, the hardness of the porcelain gold coating formed of the porcelain gold powder is preferred.
較佳地，以每一瓷金顆粒的總重為100wt%，硼化鎢的含量範圍為27至30wt%。當硼化物的含量範圍為27至30wt%時，由瓷金粉末所形成的瓷金塗層的強度較佳。 Preferably, the total weight of each porcelain gold particle is 100% by weight, and the content of tungsten boride is in the range of 27 to 30% by weight. When the content of the boride is in the range of 27 to 30% by weight, the strength of the porcelain gold coating formed of the porcelain gold powder is preferred.
較佳地，其中，以每一瓷金顆粒的總重為100wt%，鈷的含量範圍為4至6wt%。當鈷的含量小於4wt%時，低熔點(1495℃)的黏結金屬不足。當鈷的含量大於6wt%時，由瓷金粉末所形成的瓷金塗層易受熔融鋅腐蝕。 Preferably, wherein the total weight of each of the porcelain gold particles is 100% by weight, and the content of cobalt ranges from 4 to 6% by weight. When the content of cobalt is less than 4% by weight, the low melting point (1495 ° C) of the binder metal is insufficient. When the content of cobalt is more than 6% by weight, the porcelain gold coating formed of the porcelain gold powder is susceptible to corrosion by molten zinc.
較佳地，以每一瓷金顆粒的總重為100wt%，鉻的含量範圍為4至6wt%。當鉻的含量範圍小於4wt%時，瓷金塗層中沒有足夠的鉻可形成Cr2O3，從而使瓷金塗層抗熔融鋅腐蝕的效果較差。當鉻的含量範圍大於6wt%時，因高熔點(1900℃)的鉻過多，所以不易燒結成瓷金顆粒。 Preferably, the total weight of each of the porcelain gold particles is 100% by weight, and the content of chromium ranges from 4 to 6% by weight. When the content of chromium is less than 4% by weight, there is not enough chromium in the porcelain gold coating to form Cr 2 O 3 , so that the effect of the porcelain gold coating against molten zinc corrosion is poor. When the content of chromium is more than 6% by weight, since the chromium having a high melting point (1900 ° C) is excessive, it is difficult to be sintered into porcelain gold particles.
較佳地，以每一瓷金顆粒的總重為100wt%，碳化鎢的含量範圍為60wt%至63wt%，硼化鎢的含量範圍為27wt%至30wt%，鈷的含量範圍為4wt%至6wt%，以及鉻的含量範圍為4wt%至6wt%。更佳地，以每一瓷金顆粒的總重為100wt%，碳化鎢的含量範圍為62.8wt%，硼化鎢的含量範圍為27.2wt%，鈷的含量範圍為6wt%，鉻的含量範圍為4wt%。 Preferably, the total weight of each porcelain gold particle is 100 wt%, the content of tungsten carbide ranges from 60 wt% to 63 wt%, the content of tungsten boride ranges from 27 wt% to 30 wt%, and the content of cobalt ranges from 4 wt% to 6 wt%, and chromium content ranges from 4 wt% to 6 wt%. More preferably, the total weight of each porcelain gold particle is 100 wt%, the content of tungsten carbide is 62.8 wt%, the content of tungsten boride is 27.2 wt%, the content of cobalt is 6 wt%, and the content of chromium is It is 4 wt%.
該瓷金粉末包含：CoWB、WC、W2CoB2、W6C2.54、Cr7C3、Cr7.55B3O9.91。 The cermet powder comprising: CoWB, WC, W 2 CoB 2, W 6 C 2.54, Cr 7 C 3, Cr 7.55 B 3 O 9.91.
較佳地，該瓷金塗層包含：WC、W2CoB2、W6C2.54、CrO。 Preferably, the porcelain gold coating comprises: WC, W 2 CoB 2 , W 6 C 2.54 , CrO.
本發明瓷金塗層可做為熱浸鍍鋅槽內的輥輪的表面。 The porcelain gold coating of the present invention can be used as the surface of a roller in a hot dip galvanizing bath.
本發明將就以下實施例來作進一步說明，但應瞭解的是，該實施例僅為例示說明之用，而不應被解釋為本發明實施之限制。 The present invention will be further illustrated by the following examples, but it should be understood that this embodiment is intended to be illustrative only and not to be construed as limiting.
<實施例><Example>
[實施例1]瓷金塗層[Example 1] Porcelain gold coating
提供一包含複數個瓷金顆粒的瓷金粉末，其中每一瓷金顆粒含有碳化鎢、碳化硼、鈷、鉻及鈷-鉻合金，且鈷-鉻合金的表面積與該瓷金顆粒的表面積的比值為30%，平均粒徑範圍為20μm至53μm，鬆裝密度為3.3g/cm3至3.9g/cm3。 Providing a porcelain gold powder comprising a plurality of porcelain gold particles, wherein each of the porcelain gold particles comprises tungsten carbide, boron carbide, cobalt, chromium and a cobalt-chromium alloy, and a surface area of the cobalt-chromium alloy and a surface area of the porcelain gold particles The ratio was 30%, the average particle diameter ranged from 20 μm to 53 μm, and the bulk density was from 3.3 g/cm 3 to 3.9 g/cm 3 .
接著在三個輥輪材(尺寸：25x25x7mm，材質：SC50碳鋼)上，分別以該瓷金粉末，配合使用高速火焰熔射(HVOF)及三種不同的熔射條件形成三個瓷金塗層。其中，高速火焰熔射是使用熱噴塗機(廠商型號：Sulzer Metco Wokajet-440，槍筒長度：152.4mm)，瓷金粉末的供給量為40g/min，噴塗距離為380mm，以及三種熔射條件分別為：中溫高速(氧流量：1046L/min，煤油流量：0.365L/min)、中溫低速(氧流量：893L/min，煤油流量：0.365L/min)，及高溫中速(氧流量：963L/min，煤油流量：0.438L/min)。並檢測所得到的三種瓷金塗層，檢測結果由表1所示。 Then, on the three roller materials (size: 25x25x7mm, material: SC50 carbon steel), three porcelain gold coatings were formed by using the porcelain gold powder together with high-speed flame spraying (HVOF) and three different spraying conditions. . Among them, high-speed flame spraying is the use of thermal spraying machine (manufacturer model: Sulzer Metco Wokajet-440, barrel length: 152.4mm), porcelain gold powder supply is 40g / min, spraying distance is 380mm, and three kinds of spraying conditions They are: medium temperature high speed (oxygen flow rate: 1046L/min, kerosene flow rate: 0.365L/min), medium temperature low speed (oxygen flow rate: 893L/min, kerosene flow rate: 0.365L/min), and high temperature medium speed (oxygen flow rate) : 963 L / min, kerosene flow: 0.438 L / min). The three porcelain gold coatings obtained were tested, and the test results are shown in Table 1.
[實施例2至3及比較例1至4]瓷金塗層[Examples 2 to 3 and Comparative Examples 1 to 4] Porcelain Gold Coating
實施例2至3及比較例1至4的瓷金塗層是以與實施例1相同的方式製備，差別在於使用不同的瓷金粉 末，如表1所示。 The porcelain gold coatings of Examples 2 to 3 and Comparative Examples 1 to 4 were prepared in the same manner as in Example 1 except that different porcelain gold powders were used. Finally, as shown in Table 1.
<檢測項目><test item>
1.鈷-鉻合金的表面積與瓷金顆粒的表面積的比值 1. The ratio of the surface area of the cobalt-chromium alloy to the surface area of the porcelain gold particles
取實施例1至3及比較例1至4中使用的瓷金粉末，並以掃描式電子顯微鏡(廠商型號：JOEL JSM-6300)分析每一瓷金粉末中的瓷金顆粒的元素分布(element mapping)，得到瓷金顆粒的元素分布照片。在每一張瓷金顆粒的元素分布照片中，每一瓷金顆粒中鈷元素跟鉻元素重疊分布的區域，即為鈷元素及鉻元素同時存在的鈷-鉻合金。以二維方格線劃在元素分布照片上，估算每一瓷金顆粒的鈷-鉻合金的表面積，以及每一瓷金顆粒的表面積。將每一瓷金顆粒的鈷-鉻合金的表面積除以瓷金顆粒的表面積，即為每一瓷金顆粒的鈷-鉻合金的表面積與瓷金顆粒的表面積的比值。 The porcelain gold powders used in Examples 1 to 3 and Comparative Examples 1 to 4 were taken, and the element distribution of the porcelain gold particles in each porcelain gold powder was analyzed by a scanning electron microscope (manufacturer model: JOEL JSM-6300) (element Mapping), to obtain a photo distribution of the elements of the porcelain gold particles. In the photo distribution of each porcelain gold particle, the region in which the cobalt element overlaps with the chromium element in each porcelain gold particle is a cobalt-chromium alloy in which cobalt and chromium are simultaneously present. The surface area of the cobalt-chromium alloy of each porcelain gold particle and the surface area of each porcelain gold particle are estimated by drawing a two-dimensional grid line on the element distribution photograph. The surface area of the cobalt-chromium alloy of each porcelain gold particle is divided by the surface area of the porcelain gold particles, which is the ratio of the surface area of the cobalt-chromium alloy of each porcelain gold particle to the surface area of the porcelain gold particles.
2.瓷金顆粒的鬆裝密度 2. The bulk density of porcelain gold particles
使用霍爾流量計(Hall flowmeter)，並以ASTM B212標準方法分別量測實施例1至3及比較例1至4中所使用的瓷金粉末的鬆裝密度。 The bulk density of the porcelain gold powders used in Examples 1 to 3 and Comparative Examples 1 to 4 was measured using a Hall flowmeter and the ASTM B212 standard method, respectively.
3.瓷金顆粒的粒徑 3. The particle size of porcelain gold particles
將實施例1至3及比較例1至4中所使用的瓷金粉末分別與水混合得到水溶液，將每一水溶液以雷射光散射法分析瓷金粉末的粒徑分布，即為瓷金顆粒的粒徑。 The porcelain gold powders used in Examples 1 to 3 and Comparative Examples 1 to 4 were respectively mixed with water to obtain an aqueous solution, and each aqueous solution was analyzed by laser light scattering method to analyze the particle size distribution of the porcelain gold powder, that is, the porcelain gold particles. Particle size.
4.噴塗連續性 4. Spray continuity
在實施例1至3及比較例1至4中，以高速火焰熔射形成瓷金塗層的過程包含多道的噴塗程序，在每一道噴塗程序完成並降溫冷卻後，才能再進行下一道的噴塗程序，並重覆上述的噴塗程序，以堆疊至瓷金瓷層所需的厚度。若下一道的噴塗程序會使上一道程序形成的瓷金塗層剝落，則噴塗連續性不佳。 In Examples 1 to 3 and Comparative Examples 1 to 4, the process of forming a porcelain gold coating by high-speed flame spraying includes a multi-pass spraying process, and after each spraying process is completed and cooled down, the next one can be performed. Spray the procedure and repeat the spray procedure described above to stack to the desired thickness of the porcelain gold layer. If the next spray procedure causes the porcelain gold coating formed by the previous procedure to peel off, the spray continuity is poor.
5.瓷金塗層厚度 5. Porcelain gold coating thickness
將實施例1至3及比較例1至4的瓷金塗層分別製做成剖面試片，並以掃描式電子顯微鏡(廠商型號：JOEL JSM-6300)量測厚度。 The porcelain gold coatings of Examples 1 to 3 and Comparative Examples 1 to 4 were separately prepared into cross-section test pieces, and the thickness was measured by a scanning electron microscope (manufacturer model: JOEL JSM-6300).
6.瓷金塗層的維氏硬度 6. Vickers hardness of porcelain gold coating
使用維氏硬度計(Vickers hardness tester，廠商：Shimadzu公司，型號：HVM-1)，以鑽石角錐壓頭(diamond pyramid indenter)，在荷重為300克下持續15秒量測實施例1至3及比較例1至4的瓷金塗層的維氏硬度。 Examples 1 to 3 were measured using a Vickers hardness tester (manufactured by Shimadzu Corporation, model: HVM-1) with a diamond pyramid indenter at a load of 300 g for 15 seconds. The Vickers hardness of the porcelain gold coating of Comparative Examples 1 to 4.
7.瓷金塗層孔隙率 7. Porcelain gold coating porosity
將實施例1至3及比較例1至4的瓷金塗層分別製做成剖面試片，並分別以掃描式電子顯微鏡觀察，每一瓷金塗層照10張以上的的剖面照片，再用影像處理軟體photoimpact計算單位面積中黑色孔洞的面積，即為瓷金塗層孔隙率。 The porcelain gold coatings of Examples 1 to 3 and Comparative Examples 1 to 4 were separately formed into cross-section test pieces, and each of them was observed by a scanning electron microscope, and each porcelain gold coating was taken as a cross-sectional photograph of 10 or more pieces, and then The area of the black hole in the unit area is calculated by the image processing software photoimpact, which is the porosity of the porcelain gold coating.
由表1的結果可知，實施例1至3因使用在每一瓷金顆粒中鈷-鉻合金的表面積與該瓷金顆粒的表面積的比值為20%至40%，以及每一瓷金顆粒的粒徑範圍為20 μm至53μm的瓷金粉末，並配合高速火焰熔射，使得所形成的的瓷金塗層具有150μm以上的厚度。 From the results of Table 1, it is known that Examples 1 to 3 have a ratio of the surface area of the cobalt-chromium alloy to the surface area of the porcelain gold particles in each of the porcelain gold particles of 20% to 40%, and each of the porcelain gold particles. Particle size range is 20 The porcelain gold powder of μm to 53 μm is combined with high-speed flame spraying so that the formed porcelain gold coating has a thickness of 150 μm or more.
比較例1至3因使用在每一瓷金顆粒中鈷-鉻合金的表面積與該瓷金顆粒的表面積的比值為3%至16%的瓷金粉末，導致無法在輥輪材上形成瓷金塗層。 Comparative Examples 1 to 3 resulted in the inability to form porcelain gold on the roll material because the ratio of the surface area of the cobalt-chromium alloy to the surface area of the porcelain gold particles in each of the porcelain gold particles was 3% to 16%. coating.
比較例4因使用在每一瓷金顆粒的粒徑範圍為20μm至74μm的瓷金粉末，導致無法在輥輪材上形成厚度為150μm以上的瓷金塗層。 In Comparative Example 4, since a porcelain gold powder having a particle diameter ranging from 20 μm to 74 μm per porcelain gold particle was used, it was impossible to form a porcelain gold coating having a thickness of 150 μm or more on the roller material.
綜上所述，本發明藉由選用每一瓷金顆粒中鈷-鉻合金的表面積與該瓷金顆粒的表面積的比值為20%至40%，以及每一瓷金顆粒的粒徑範圍為20μm至53μm的瓷金粉末，並配合高速火焰熔射，從而使得所形成的瓷金塗層具有150μm以上的厚度，故確實能達成本發明之目的。 In summary, the present invention selects the ratio of the surface area of the cobalt-chromium alloy to the surface area of the porcelain gold particles in each porcelain gold particle to be 20% to 40%, and the particle size range of each porcelain gold particle is 20 μm. The porcelain gold powder to 53 μm is blended with high-speed flame so that the formed porcelain gold coating has a thickness of 150 μm or more, so that the object of the present invention can be achieved.
惟以上所述者，僅為本發明之較佳實施例而已，當不能以此限定本發明實施之範圍，即大凡依本發明申請專利範圍及專利說明書內容所作之簡單的等效變化與修飾，皆仍屬本發明專利涵蓋之範圍內。 The above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, that is, the simple equivalent changes and modifications made by the patent application scope and patent specification content of the present invention, All remain within the scope of the invention patent.
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