CN1771002A - 带耐失泽性陶瓷涂层的食具及制造方法 - Google Patents
带耐失泽性陶瓷涂层的食具及制造方法 Download PDFInfo
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- CN1771002A CN1771002A CNA2004800078443A CN200480007844A CN1771002A CN 1771002 A CN1771002 A CN 1771002A CN A2004800078443 A CNA2004800078443 A CN A2004800078443A CN 200480007844 A CN200480007844 A CN 200480007844A CN 1771002 A CN1771002 A CN 1771002A
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- 238000005524 ceramic coating Methods 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000000919 ceramic Substances 0.000 claims abstract description 56
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010936 titanium Substances 0.000 claims description 114
- 229910052719 titanium Inorganic materials 0.000 claims description 111
- 229910052782 aluminium Inorganic materials 0.000 claims description 107
- 238000000576 coating method Methods 0.000 claims description 48
- 239000011248 coating agent Substances 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 33
- 229910001220 stainless steel Inorganic materials 0.000 claims description 29
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- 238000005494 tarnishing Methods 0.000 claims description 28
- 238000000151 deposition Methods 0.000 claims description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 16
- 235000013305 food Nutrition 0.000 claims description 16
- 229910045601 alloy Inorganic materials 0.000 claims description 12
- 239000000956 alloy Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 230000008021 deposition Effects 0.000 claims description 11
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- 239000011651 chromium Substances 0.000 claims description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- 238000005240 physical vapour deposition Methods 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims 1
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- 229910052802 copper Inorganic materials 0.000 description 31
- 239000007789 gas Substances 0.000 description 26
- 239000004411 aluminium Substances 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000010411 cooking Methods 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
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- 238000012360 testing method Methods 0.000 description 7
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- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910001018 Cast iron Inorganic materials 0.000 description 4
- 229910010037 TiAlN Inorganic materials 0.000 description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
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- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 4
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- 238000007254 oxidation reaction Methods 0.000 description 4
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- 206010027146 Melanoderma Diseases 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
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- 238000012545 processing Methods 0.000 description 3
- 244000131522 Citrus pyriformis Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910010038 TiAl Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
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- ALKZAGKDWUSJED-UHFFFAOYSA-N dinuclear copper ion Chemical compound [Cu].[Cu] ALKZAGKDWUSJED-UHFFFAOYSA-N 0.000 description 2
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
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- 238000012546 transfer Methods 0.000 description 2
- 239000010963 304 stainless steel Substances 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
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- 239000004744 fabric Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000011824 nuclear material Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
- C23C14/025—Metallic sublayers
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- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47J—KITCHEN EQUIPMENT; COFFEE MILLS; SPICE MILLS; APPARATUS FOR MAKING BEVERAGES
- A47J36/00—Parts, details or accessories of cooking-vessels
- A47J36/02—Selection of specific materials, e.g. heavy bottoms with copper inlay or with insulating inlay
- A47J36/04—Selection of specific materials, e.g. heavy bottoms with copper inlay or with insulating inlay the materials being non-metallic
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- C23C14/0021—Reactive sputtering or evaporation
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Abstract
一种具有热稳定性的彩色耐失泽性陶瓷涂层的食具制品,其中所述陶瓷涂层使得食具制品可以与热源如气体火焰或电炉的加热元件直接接触。本发明的食具制品包括具有内食物接触面(110)和外热源接触面(115)的金属食具制品(105);沉积在一部分外热源接触面(115)上的粘结层(120);相邻沉积在一部分粘结层上的第一陶瓷层(125),该第一陶瓷层(125)选自(Ti,Al)N、(Ti,Al)CN、(Ti,Al,X)N或(Ti,Al,X)CN。可以在一部分第一陶瓷层上相邻沉积TiCN表层。任选地有与粘结层相邻沉积并位于第一陶瓷层之下的交替的第三陶瓷层和第四陶瓷层,其中第三陶瓷层选自(Ti,Al)N、(Ti,Al)CN、(Ti,Al,X)N或(Ti,Al,X)CN,第四陶瓷层选自TiN、TiCN、XN或XCN。需要时,交替层可以任意重复多次。还公开了制造这种食具的方法。
Description
本发明一般性地涉及一种带耐失泽性涂层的食具制品,尤其是涉及一种在外热源接触表面上具有热稳定的耐失泽性陶瓷涂层的食具制品,以及制造这种食具制品的方法。
陶瓷涂层,如TiN、ZrCN和TiCN,由于其装饰性的外观和耐失泽性能,已经被用于包括龙头、门用五金、标牌、各种建筑应用以及其它行业在内的各种应用。这些应用不涉及与热源例如气体火焰或电加热元件直接接触。
陶瓷涂层已经被用作不粘涂层或被用于炊具的食物接触面上的防粘,例如美国专利US 5,447,803、6,197,438和6,360,423。不过,这些涂层不是用在炊具的热源接触面上。此外,美国专利US 6,197,438指出,包括TiN、TiCN、ZrN、CrN和AlTiN在内的各种陶瓷涂层的火焰颜色稳定性都很差。但没有说明进行了何种测试或测试的施行条件。
炊具可以由包括铸铁、铜、铝和钢在内的各种材料制造。每种炊具都具有其优缺点。
经过老化的铸铁炊具具有坚硬、耐磨的表面。不过,铸铁易于生锈,所以必须对其进行仔细清洗以避免炊具表面损坏。此外,酸性食物可能引起铁从表面浸出,在某些情况下这会导致健康问题。
铜炊具具有出色的传热特性。不过,由于它比其它炊具材料如铸铁或不锈钢软得多,所以很容易刮伤。铜还很容易氧化,这会导致失泽。铜可以通过抛光来除去锈蚀,但需要很多努力来保持表面光洁度。
铝炊具具有出色的传热特性。不过,铝也很容易失泽。它不能抛光,但它必须定期擦洗,因为炉顶燃烧物和食物颗粒很容易使其变色。
不锈钢炊具应用广泛。它以其强度和耐用性而著称。不锈钢相对易于清洁,并且它能比铜更好地保持光泽。不过,不锈钢是不良导热体。为克服其不良导热性,经常向不锈钢壶或锅的底部添加铝盘或铜盘。在很多情况下,食具的底部是铜制的或镀铜的。或者,在铝层或铜层上覆盖不锈钢以制成一种多层制品。不过,如果不锈钢锅具有暴露在外的铜,则必须对铜进行抛光以保持其光泽。
尽管许多人喜欢铜炊具的外观,但保持光洁度所需的时间和精力却阻止了许多人使用它。因此,需要一种易保持且耐失泽性的食具用涂层。
本发明通过提供一种在外热源接触面上具有热稳定性彩色的耐失泽性陶瓷涂层的食具制品来满足此需要。所谓“食具”是指炊具、包括刀具和其它手动食品加工用具(如滤器、筛网等等)在内的食品准备用具、食品提供用具(如盘、碗等等)以及用于进食的用具。“炊具”是指用于炉顶烹调的壶和锅、烤盘、平底锅、烤架、烹调用具(如匙、刮刀等等)以及用于烹饪食物的食品准备器件(如电煎锅、饭锅等等)。“耐失泽性”是指陶瓷涂层在空气环境下能抗失泽并且能够承受直接加热而涂层不失泽或剥落。
在一个实施方案中,本发明的食具制品包括一种具有内食物接触表面和外热源接触表面的金属食具制品;粘结层沉积在一部分外热源接触表面上;第一陶瓷层相邻沉积在一部分粘结层上,第一陶瓷层选自(Ti,Al)N、(Ti,Al)CN、(Ti,Al,X)N或(Ti,Al,X)CN。其中“沉积”是指直接沉积在在先层上而没有任何插入层。而“相邻沉积”是指紧接着在先层沉积但并非必须直接沉积在在先层上。它可以直接沉积在在前层上,或者在彼此相邻沉积的层之间可以有一个或多个插入层。“(Ti,Al,X)N或(Ti,Al,X)CN”是指钛和铝作主要组分并具有少量其它元素(“X”)的氮化物或碳氮化物合金。其它元素包括但不限于铬和钇。(Ti,Al,X)N或(Ti,Al,X)CN合金包括但不限于超晶格结构的(Ti,Al)N/XN或(Ti,Al)CN/XN。
需要的话,在一部分第一陶瓷层上可以沉积TiCN表层,以获得铜风格的颜色。“铜风格的颜色”是指具有铜外观的颜色,包括例如与青铜、玫瑰金或铜类似的颜色。
任选地可以有一个与粘结层相邻沉积并位于第一陶瓷层之下的第二陶瓷层,该第二陶瓷层选自TiN、TiCN、XN或XCN。
任选地可以有与粘结层相邻沉积并位于第一陶瓷层之下的交替的第三陶瓷层和第四陶瓷层,其中第三陶瓷层选自(Ti,Al)N、(Ti,Al)CN、(Ti,Al,X)N、或(Ti,Al,X)CN,第四陶瓷层选自TiN、TiCN、XN或XCN。如果需要,交替层可以重复多次。
金属食具制品可以由包括但不限于钢、不锈钢、钛、覆层材料或它们的合金的材料制造。
粘结层可以由包括但不限于钛、铬、锆或它们的合金的金属制造。
本发明的另一方面是制造具有热稳定性彩色的耐失泽性陶瓷涂层的食具制品的方法。该方法包括:提供具有内食物接触表面和外热源接触面的金属基材;在一部分外热源接触表面上沉积粘结层;与一部分粘结层相邻沉积第一陶瓷层,该第一陶瓷层选自(Ti,Al)N、(Ti,Al)CN、(Ti,Al,X)N或(Ti,Al,X)CN;并将金属基材制成食具制品。金属基材既可以在沉积涂层之前也可以在其之后制成食具制品。
所述各层可以通过包括但不限于物理汽相沉积方法的方法沉积。如果需要,可以通过阴极弧沉积工艺沉积所述层。
图1是本发明的食具制品的一个实施方案的横截面图。
图2是本发明的食具制品的另一实施方案的横截面图。
图3是可用于本发明的阴极弧沉积室的示意图。
图4是一个根据本发明进行涂覆并浅拔形成平底锅的金属坯板的示意图。
氮化钛铝((Ti,Al)N)涂层由于其高抗氧化性和耐磨性常被用于干式高速切削加工。典型的(Ti,Al)N涂层是用50/50At%的TiAl靶沉积的。在(Ti,Al)N涂层上最高工作温度可达1450°F。(Ti,Al)N涂层很硬,根据所采用的物理汽相沉积工艺不同,其显微硬度为2600-3000HV,0.05。根据沉积条件不同,50/50(At%)的(Ti,Al)N涂层的颜色为褐色或略带紫色。
碳氮化钛(TiCN)是非常硬的陶瓷涂层,显微硬度在3000HV,0.05以上。通过控制氮气对乙炔或甲烷的比例,TiCN的颜色可以为从铜风格的颜色到黑色。
如果需要,本发明的陶瓷涂层结合了(Ti,Al)N、(Ti,Al)CN、(Ti,Al,X)N和(Ti,Al,X)CN涂层的高抗氧化性和抗磨性以及TiCN涂层的铜风格的颜色特性,用于具有耐失泽性外热源接触面的食具。
如果使用表层,则(Ti,Al)N略呈紫色的颜色可以充当TiCN表层的基础。
本发明的涂层的总厚度根据食具应用的不同通常在约0.5-约20微米的范围。如果使用,则TiCN表层通常小于约2.0微米。
本发明的陶瓷涂层在正常烹调条件下可以直接接触气体火焰和电炉加热元件而不会烧伤或失泽。TiCN的热极限是750°F,下面的陶瓷层(Ti,Al)N可以经受最高达1450°F的温度。在烹调中,即使内容物处于沸腾条件下,它们实际上也能显著地冷却炊具。炊具底部的实际温度可以在750°F之下。此外,由覆层材料制造的炊具要求热源温度低于900°F以避免不锈钢和铝(构成覆层复合材料)分离。建议在中或低档下加热。在本发明中,由于TiCN表层很薄,所以热源既会与TiCN表层又会与下面的陶瓷层反应。本发明的多层陶瓷涂层以TiCN作表层,适于在中火档烹调条件下直接加热。直接接触热源的表面温度通常低于750°F。在失去表涂层TiCN的情况下,相似颜色的(Ti,Al)N可以防止食具失泽。
如果需要,第一陶瓷层(Ti,Al)N、(Ti,Al)CN、(Ti,Al,X)N或(Ti,Al,X)CN可以是表层。涂层的颜色可以根据该层的组成和沉淀条件而改变。如本领域技术人员所公知,通过控制加工和通入不同的气体,(Ti,Al)N和(Ti,Al)CN的颜色可以从紫色到烟灰色到黑色变化。通过向(Ti,Al)N或(Ti,Al)CN中添加其它元素如铬,形成例如(Ti,Al,Cr)N或(Ti,Al,Cr)CN,这些涂层的抗氧化能力能得到进一步提高。如所述,如本领域技术人员所公知,通过控制沉积过程这些涂层可以具有不同的颜色。(Ti,Al)N、(Ti,Al)CN、(Ti,Al,X)N或(Ti,Al,X)CN表层设计用于要求在低于1450°F的高温下应用的热源。
(Ti,Al)N/TiN、(Ti,Al)CN/TiCN、(Ti,Al,X)N/XN或(Ti,Al,X)CN/XCN的交替序列是合乎需要的,因为它能进一步提高涂层的硬度和热稳定性。这使得在成形过程中冲拔带薄多层镀层的金属板而不使涂层破裂更加容易。各交替层的典型厚度在约0.1-约1.0微米的范围。
图1示出了本发明的食具制品的一个实施方案100的截面图。这是一个金属食具制品105,例如平底锅。金属食具制品105具有内食物接触面110和外热源接触面115。金属食具制品105可以由包括但不限于钢、不锈钢、钛、覆层材料或它们的合金的各种金属制造。金属食具制品可以由固体金属或固体合金制造,或者它可以是覆层材料,例如具有金属表面的多层结构。所述多层结构的例子包括但不限于包不锈钢的铝或铜、具有等离子体喷涂不锈钢涂层的铝、或围绕非金属的核材料如石墨的金属外层。
在一部分外热源接触面115上沉积了粘结层120。粘结层的厚度通常小于约1.0微米。粘结层可以由包括但不限于钛、铬、锆或它们的合金的金属制造。
在一部分粘结层120邻接沉积了第一陶瓷层125。第一陶瓷层125可以为(Ti,Al)N、(Ti,Al)CN、(Ti,Al,X)N或(Ti,Al,X)CN。第一陶瓷层125通常在约0.5-约10微米的范围之内。第一陶瓷层125提供了高抗氧化性和防失泽特性,即使是在直接暴露于高气体火焰或接触电炉的高温加热单元时亦是如此。如果有表层的话,第一陶瓷层还向表层提供了基体。尽管图中显示在此实施方案中第一陶瓷层125位于粘结层上,但如果需要的话在粘结层120和第一陶瓷层125之间可以有一个或多个插入层。
在一部分第一陶瓷层125上沉积有表层TiCN 130。TiCN层130的厚度通常在约0.1-约2.0微米的范围之内。如果需要的话,TiCN层130可以向涂层提供铜风格的颜色。如本领域技术人员所公知,铜风格的颜色是由所期望的颜色和沉积工艺如氮对乙炔或甲烷的比例、沉积温度和真空度决定的。
尽管图中显示在此实施方案中TiCN层130位于第一陶瓷层125上,但如果需要的话在第一陶瓷层125和TiCN层130之间可以有一个或多个插入层。
图2示出了本发明的食具制品的另一实施例200的横截面。它是具有内食物接触面210和外热源接触面215的金属食具制品205。在一部分外热源接触面215上沉积了粘结层220。
具有交替层225、230、235、240、245、250。层225、235、245可以为TiN、TiCN、XN或XCN。尽管图中显示在此实施方案中层225位于粘结层220之上,但在粘结层220和层225之间可以有一个或多个插入层。
层230、240、250可以为(Ti,Al)N、(Ti,Al)CN、(Ti,Al,X)N或(Ti,Al,X)CN。通过控制沉积工艺和气体混合物,可以获得一个热稳定的陶瓷涂层。
层225、230、235、240、245、250的厚度通常在约0.1-约1.0微米的范围之内。
其中每个层都可以沉积在食具制品的整个外热源接触面,如锅底和侧壁,或只是沉积在它的一部分上,例如只沉积在锅底上。
所述涂覆层可以利用物理汽相沉积工艺如蒸发、溅射、阴极弧或离子束,或其它适合的工艺沉积。
下面将举例说明一种在食具制品上沉积涂层的方法。如本领域技术人员所公知,也可以采用其它方法或步骤。
食具制品可以先成型然后涂覆,也可以先涂覆金属平板然后再制成平底锅。下面将对用阴极弧沉积涂覆金属板然后形成平底锅的方法进行描述。
必要时,金属板在沉积之前可以先抛光以产生一个平滑表面。如本领域技术人员所知,可以使用抛光或研磨剂、或其它抛光介质。适合的光洁度的例子包括但不限于#4光洁度(表面光洁度为约10微英寸)和#8无方向性镜面抛光表面(表面光洁度为约2-3微英寸)。
然后对板进行彻底清洗和干燥以除去所有油脂、抛光残余物、松散的和嵌入的颗粒、氧化物、盐残留物或其它异物。典型的清洗包括水清洗系统结合超声清洗。
将板装入适合的夹具,并放入如图3所示的沉积室300的轨道。如图所示,板305在沉积过程中可以经受一重或双重轨道旋转。转台310可以旋转所有的板,如果需要,也可以旋转单独的板305。
如图3所示,在室内放置了适合的靶315和320。例如,50%钛/50%铝(At%)的压制金属粉末靶320可以与纯钛的金属靶315一起使用。图3的示意图是当所有靶315和320在沉积过程中都工作时形成(Ti,Al)N/TiN的超晶格结构层的一种典型模型。合金靶还可以是与纯金属靶一起使用的钛、铝和X的组合以及本领域技术人员所知的其它组合的压制金属粉末。靶的数量和类型取决于沉积室的尺寸和所要沉积的涂层。
将沉积室抽至约10-3Pa的压力。根据板的厚度、尺寸、板的数量以及材料的种类不同,将板加热至约350°F-450°F的温度。
通过向板上施加800-1200V的负偏压产生辉光放电,对板进行微观清洗。
首先沉积粘结层。将适合的靶(例如Ti)置于高温下,并在约10-2Pa的真空度下用偏压为约600-1000V的离子(Ti+)对锅进行轰击,形成厚度通常小于约1.0微米的粘结层。
打开钛铝靶,并关闭钛靶。然后向系统中通入氮气,以形成(Ti,Al)N层。所施加的负偏压在约0.4-1.5Pa的真空度下为约80-200V。(Ti,Al)N层能提供高耐磨性和高抗氧化性。
关闭TiAl靶、打开钛靶。除已经存在的氮气之外,再引入甲烷或乙炔,以在约80-200V的偏压下沉积TiCN层。TiCN层能提供铜风格的颜色。通过变化在物理汽相沉积过程中的工艺条件和氮气对甲烷或乙炔的比可以改变所述颜色。如本领域技术人员所公知,(Ti,Al)N层和TiCN层的组成可以通过改变用于各个层的靶的数量和种类以及控制沉积过程来改变。在沉积的后期沉积温度可以提高至约600-900°F。
如果需要可以在各个层之间加入其它层。可以沉积(Ti,Al)N和TiN;(Ti,Al)CN和TiCN;(Ti,Al,X)N和XN;或(Ti,Al,X)CN和XCN的交替层。如果需要,(Ti,Al,X)N或(Ti,Al,X)CN可以是超晶格结构层。
可以在板的涂覆表面上施加聚氯乙烯薄膜层(或其它适合的保护层),以防止涂层在成形过程中被破坏。
通过涂覆坯件和将坯件浅拔成平底锅来制造食具制品的方法非常适合于具有带圆角的外形的食具制品,以避免圆角区域的表面结构在冲拔过程中被改变。在此方法中,表面光洁度通常在10-16微英寸的范围之内。所述小于10微英寸的高度抛光表面光洁度可被用于具有非常大的圆角的食具的浅拔。
试验1
用上述方法对0.8英寸厚8″×8″的304不锈钢板坯进行涂覆。所述板坯具有工业#4毛面光洁度和#8镜面光洁度。涂覆的板坯被拔成直径6″的平底锅。
图4a显示了经涂覆的坏件400。坯件405具有在形成平底锅之后会与食物接触的表面410和相对的在形成锅之后会充当外热源接触面的面415。涂层420形成在面415上,不过未显示各个单层。直径8″的经涂覆的坯件随后被浅拔成如图4b所示的直径6″的平底锅。被涂覆表面是锅的热源接触面。侧壁430与带圆角的底435垂直。
本发明的涂层在所有表面包括圆角区域上都粘合得很好。#4表面光洁度平底锅在圆角区域与底面相比没有明显的表面结构改变。具有#8镜面的高度抛光平底锅在圆角区域显示了与底部镜面相比明显的表面结构差异。
试验2
通过用根据本发明制造的平底锅直接在气体火焰和电加热元件上烧水测试本发明的食具制品的热稳定性和耐失泽性。对炊具的涂层表面持续加热约1.5-2小时。与一般的烹调条件相比,这是一种相当苛刻的测试。重复此步骤2-3次,结果如表1所示。
实施例1和2是传统的带电镀铜的底和低侧壁的不锈钢锅。在高气体火焰上煮一小时和两个小时之后,底面显示了严重的氧化和黑色失泽斑点。两个小时之后(实施例2)锅底上变黑的氧化斑点更加严重,它是铜炊具上的典型失泽外貌。在该实施例中,失泽斑点必须进行抛光才能除去。
实施例3-10显示了本发明的涂层的性能。实施例3和4中,炊具涂覆了本发明的涂层。在实施例5-10中,对8″坯件进行了涂覆,并用涂覆的坯件制成了6″的平底锅。
在电炉加热中,加热元件的外径为大约6英寸。当6″的平底锅放在加热元件上时,锅的圆角区域直接接触外面的加热元件。加热元件在“高”档下可以达到950°F。此测试能很好地评价所形成表面(包括底、侧壁和圆角)的涂层附着力和抗失泽性。
实施例3是具有(Ti,Al)N层和TiCN表层的不锈钢碗。用此碗在低气体火焰上烧水两个小时。只有几个由气体火焰沉积的微微变黑的斑点。通过用热水和毛巾清洗,所述沉积物几乎被完全除去。
实施例4是具有(Ti,Al)N层和TiCN表层的不锈钢锅。将锅在电炉上加热1个小时,在中气体火焰上加热3小时,在低气体火焰上加热2小时,并在高气体火焰上加热1.5小时(总计7.5小时)。锅在炉栅痕周围出现了变色。变色区域是在6.5小时的加热时间内由气体火焰与炉栅上的污垢反应所沉积的。拿抹布用热肥皂水清洗锅,在热水中漂洗,彻底干燥,只使用毛巾擦掉所述污斑和炉栅痕。用这样的方式清洗之后,炉栅痕几乎完全消失。锅仍然保持其铜风格的颜色。
实施例5是带(Ti,Al)N层和具有铜风格的颜色的TiCN表层的不锈钢平底锅。在设置在高温档的电炉上用此锅烧水。电加热元件与锅底相接触。加热两个小时之后,接触加热元件的某些区域的底面出现了微微的黑环。这可以用热肥皂水和干毛巾清洗。尽管锅的圆角区域与加热元件直接接触,且加热元件的温度可达950°F,但此区域并没有变色。
实施例6是带(Ti,Al)N外涂层的不锈钢平底锅。在设置在高温档的电炉上烧水。锅底的外观基本没有变化。用WindexTM清洗剂对其进行清洗。
实施例7使用与实施例6相同的锅,但将它在高气体火焰上进行加热。在烧水两个小时之后,锅底上在炉栅周围显示了气体火焰沉积物。这些沉积物很容易用热肥皂水或Bar KeepersTM清洗剂除去。锅底仍保持其外观。
实施例8和9是同一具有玫瑰金色的TiCN外涂层的平底锅。在设置在高温档的电炉上(实施例8)和在设置为中火的煤气炉上(实施例9)用该锅烧水1.5小时。在电炉上加热的情形只显示了几个小黑斑。在气体火焰上加热的情形显示了一些变黑的褐色斑点。这些斑点可以用热肥皂水和干毛巾或用WindexTM清洗剂轻易洗掉。
实施例10是镀有带银灰色(Ti,Al,Cr)N表层的多层涂层的预成形锅。在高气体火焰上烧水2小时。锅底上显示了一些火焰沉积物,用热肥皂水或Bar Keepers清剂可洗净。
在这些实施例中,加热后都显示了气体火焰沉积或炉栅痕。为表明所述沉积物或炉栅痕不是失泽或氧化,在实施例11中,平底锅(与实施例7中所用锅相同)不是直接放在炉栅上,而是放在轴上。用气体火焰对锅底进行加热,其中锅不与任何东西发生物理接触。由于气体火焰,底面恒定在1100-1200°F的温度。加热两个小时之后,底面未发现任何变化,也没有任何气体火焰沉积物。因此,炉栅痕是由气体火焰与炉栅上的污垢反应形成的,不是失泽。
表1
实施例 | 炊具/涂层 | 表面涂层/颜色 | 烧水(小时) | 煮过后的炊具表面外观 | 热肥皂水&毛巾1 | Bar KeepersTM或檬柠汁2 | Wintex3 | 抛光4 | ||
煤气灶 | 电炉 | 底部 | 圆角区域 | |||||||
1 | 不锈钢锅底部电镀有铜 | 铜 | 1.0小时(H) | 失泽、黑斑 | X | |||||
2 | 不锈钢锅底部电镀有铜 | 铜 | 2.0小时(H) | 严重失泽、黑斑 | X | |||||
3 | 不锈钢锅/101-2 | TiCN/铜 | 2.0小时(L) | 5个小褐色斑点 | 无变化 | X | ||||
4 | 不锈钢锅/919(2) | TiCN/铜 | 1.5小时(H),3.0小时(M),2.0小时(L) | 1小时(H) | 炉栅痕 | 无变化 | X | |||
5 | 不锈钢锅/919(4) | TiCN/铜 | 2小时(H) | 一个位于与加热元件接触处微黑的环 | 无变化 | X | ||||
6 | 不锈钢锅/1029-2 | TiAlN/紫 | 2小时(H) | 少数变黑的斑点 | 无变化 | X | ||||
7 | 不锈钢锅/1029-2 | TiAlN/紫 | 2.0小时(H) | 炉栅周围有一些火焰沉积物 | 无变化 | X | X | |||
8 | 不锈钢锅/115-1 | TiCN/玫瑰金 | 1.5小时(H) | 少数小黑斑点 | 无变化 | X | ||||
9 | 不锈钢锅/115-1 | TiCN/玫瑰金 | 1.5小时(M) | 一些变黑区域/在炉栅区域无火焰沉积物 | 无变化 | X | ||||
10 | 不锈钢锅/1-14 | (Ti,Al,Cr)N/灰 | 2.0小时(H) | 炉栅周围有一些火焰沉积物 | 无变化 | X | X | |||
11 | 不锈钢锅/1029-2 | TiAlN/紫 | 2.0小时(H) | 无明显变化 | 无变化 | X |
1用热肥皂水清洗,并用毛巾擦干。
2用Bar KeepersTM清洗剂或柠檬汁清洗。
3用Windex清洗。
4用适合铜的化合物抛光。
本发明的多层陶瓷涂层提供了具有热稳定的颜色的涂层。即使是长时间直接暴露于气体火焰和电加热元件,该涂层也能显示高抗氧化性和抗失泽能力。这种食具制品容易清洗,并能保持其铜风格的颜色或其它颜色。本发明的多层涂层在成型过程中能在圆角区域很好地粘合,并且在直接加热时能显示良好的耐失泽性。本发明的涂层提供了涂覆板或板坯并随后将板或坯件成型为平底锅的能力。这比涂覆单个的锅更加经济,尽管如果需要的话也可以那样做。
(Ti,Al)N、(Ti,Al)CN、(Ti,Al,X)N或(Ti,Al,X)CN表层设计用于高温加热条件。即使在高温加热条件之下陶瓷涂层也能保持其颜色(从金属色到褐色,和从紫色到黑色)。尽管某些电炉或气体火焰炉可以达到1500-1660°F,但炊具内的液体物质能显著地冷却加热面。加热面通常不会达到(Ti,Al)N涂层的热极限1450°F。因此,(Ti,Al,X)N(Ti,Al,X)CN陶瓷涂层可用于炊具工业中现有的任何热源。(Ti,Al)N层涂层和TiCN涂层表层适合于烹调时的低至中档加热条件。带(Ti,Al)N层和TiCN表层的涂层具有铜风格的颜色和耐失泽性。此涂层可用于那些传统上使用铜的炊具。
尽管为解释本发明,披露了某些代表性的实施方案和细节,但对于本领域技术人员来说,在不偏离所附权利要求所定义的本发明的范围的基础上可以对在此所公开的组成和方法作出各种改变。
Claims (20)
1.一种具有热稳定性彩色耐失泽性陶瓷涂层的食具制品,它包括:
具有内食物接触面和外热源接触面的金属食具制品;
沉积在一部分外热源接触面上的粘结层;
相邻沉积在一部分粘结层上、在粘结层与外热源接触面相对一侧上的第一陶瓷层,该第一陶瓷层选自(Ti,Al)N、(Ti,Al)CN、(Ti,Al,X)N或(Ti,Al,X)CN,其中所述陶瓷涂层是耐失泽性的且在长时间接触热源之后保持所述热稳定性的颜色。
2.权利要求1的食具制品,进一步包括相邻沉积在一部分第一陶瓷层的、在该第一陶瓷层与外热源接触面相对一侧上的TiCN表层。
3.权利要求1的食具制品,进一步包括位于粘结层和第一陶瓷层之间的第二陶瓷层,该第二陶瓷层选自TiN、TiCN、XN或XCN。
4.权利要求1的食具制品,进一步包括沉积在粘结层和第一陶瓷层之间的交替的第三陶瓷层和第四陶瓷层,其中第三陶瓷层选自(Ti,Al)N、(Ti,Al)CN、(Ti,Al,X)N或(Ti,Al,X)CN,第四陶瓷层选自TiN、TiCN、XN或XCN。
5.权利要求4的食具制品,其中每个交替层的厚度在约0.1-约1.0微米的范围之内。
6.权利要求1的食具制品,其中所述金属食具制品是由选自钢、不锈钢、钛、覆层材料或它们的合金的材料制造的。
7.权利要求1的食具制品,其中所述粘结层是选自钛、铬、锆或它们的合金的金属。
8.权利要求1的食具制品,其中所述涂层的总厚度在约0.5-约20微米的范围之内。
9.一种制造具有热稳定性彩色耐失泽性陶瓷涂层的食具制品的方法,它包括:
提供具有内食物接触面和外热源接触面的金属基材;
在一部分外热源接触面上沉积粘结层;
在粘结层与外热源接触面相对一侧的一部分粘结层上相邻沉积第一陶瓷层,该第一陶瓷层选自(Ti,Al)N、(Ti,Al)CN、(Ti,Al,X)N或(Ti,Al,X)CN;以及
将金属基材成型为食具制品,其中所述陶瓷涂层是耐失泽性的且在长时间接触热源之后保持所述热稳定性的颜色。
10.权利要求9的方法,进一步包括在一部分第一陶瓷层上沉积TiCN陶瓷表层。
11.权利要求9的方法,进一步包括在粘结层和第一陶瓷层之间沉积第二陶瓷层,该第二陶瓷层选自TiN、TiCN、XN或XCN。
12.权利要求9的方法,进一步包括在粘结层和第一陶瓷层之间沉积交替的第三陶瓷层和第四陶瓷层,其中第三陶瓷层选自(Ti,Al)N、(Ti,Al)CN、(Ti,Al,X)N或(Ti,Al,X)CN,第四陶瓷层选自TiN、TiCN、XN或XCN。
13.权利要求12的方法,其中每个交替层的厚度在约0.1-约1.0微米的范围之内。
14.权利要求9的方法,其中所述各层是通过物理汽相沉积法沉积的。
15.权利要求9的方法,其中所述各层是通过阴极弧沉积工艺沉积的。
16.权利要求9的方法,其中所述金属基材在沉积涂层之前被成型为食具制品。
17.权利要求9的方法,其中所述金属基材在沉积涂层之后被型为食具制品。
18.权利要求9的方法,其中所述金属食具制品是由选自钢、不锈钢、钛、覆层材料或它们的合金的材料制造的。
19.权利要求9的方法,其中所述粘结层是一种选自钛、铬、锆或它们的合金的金属。
20.权利要求9的方法,其中涂层的总厚度在约0.5-约20微米的范围之内。
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-
2003
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-
2004
- 2004-03-03 AT AT04716918T patent/ATE341982T1/de not_active IP Right Cessation
- 2004-03-03 EP EP04716918A patent/EP1608251B1/en not_active Expired - Lifetime
- 2004-03-03 CA CA002517011A patent/CA2517011A1/en not_active Abandoned
- 2004-03-03 DE DE602004002766T patent/DE602004002766T2/de not_active Expired - Fee Related
- 2004-03-03 WO PCT/US2004/006403 patent/WO2004084690A1/en active IP Right Grant
- 2004-03-03 JP JP2006509012A patent/JP4500807B2/ja not_active Expired - Lifetime
- 2004-03-03 CN CNB2004800078443A patent/CN100463633C/zh not_active Expired - Lifetime
-
2005
- 2005-03-28 US US11/091,274 patent/US20050170091A1/en not_active Abandoned
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102378830A (zh) * | 2009-04-07 | 2012-03-14 | 国有物资有限合伙公司 | 具有耐久和无锈蚀的多层陶瓷涂层的普通铜餐具和金属制品以及制备方法 |
CN105296919A (zh) * | 2009-04-07 | 2016-02-03 | 国有物资有限合伙公司 | 具有耐久和无锈蚀的多层陶瓷涂层的普通铜餐具和金属制品以及制备方法 |
Also Published As
Publication number | Publication date |
---|---|
JP2006521176A (ja) | 2006-09-21 |
WO2004084690A1 (en) | 2004-10-07 |
CN100463633C (zh) | 2009-02-25 |
ATE341982T1 (de) | 2006-11-15 |
JP4500807B2 (ja) | 2010-07-14 |
EP1608251A1 (en) | 2005-12-28 |
EP1608251B1 (en) | 2006-10-11 |
CA2517011A1 (en) | 2004-10-07 |
US6942935B2 (en) | 2005-09-13 |
US20050170091A1 (en) | 2005-08-04 |
US20040191579A1 (en) | 2004-09-30 |
DE602004002766D1 (de) | 2006-11-23 |
DE602004002766T2 (de) | 2007-10-04 |
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Effective date of registration: 20191115 Address after: 382 Kwun Tong Road, Kowloon, Hong Kong, China Patentee after: MEYER INTELLECTUAL PROPERTIES Ltd. Address before: Illinois, USA Patentee before: National Material L.P. |
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