CN104024179A - 透明陶瓷 - Google Patents
透明陶瓷 Download PDFInfo
- Publication number
- CN104024179A CN104024179A CN201280054455.0A CN201280054455A CN104024179A CN 104024179 A CN104024179 A CN 104024179A CN 201280054455 A CN201280054455 A CN 201280054455A CN 104024179 A CN104024179 A CN 104024179A
- Authority
- CN
- China
- Prior art keywords
- crystalline ceramics
- described crystalline
- ceramics
- particle size
- pottery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
- C04B35/111—Fine ceramics
- C04B35/115—Translucent or transparent products
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F41—WEAPONS
- F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
- F41H5/00—Armour; Armour plates
- F41H5/02—Plate construction
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/44—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/44—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminates
- C04B35/443—Magnesium aluminate spinel
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
- C04B35/486—Fine ceramics
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
- C04B35/505—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds based on yttrium oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/581—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on aluminium nitride
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62625—Wet mixtures
- C04B35/6263—Wet mixtures characterised by their solids loadings, i.e. the percentage of solids
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62695—Granulation or pelletising
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
- C04B35/645—Pressure sintering
- C04B35/6455—Hot isostatic pressing
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5427—Particle size related information expressed by the size of the particles or aggregates thereof millimeter or submillimeter sized, i.e. larger than 0,1 mm
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/549—Particle size related information the particle size being expressed by crystallite size or primary particle size
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
- C04B2235/661—Multi-step sintering
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/72—Products characterised by the absence or the low content of specific components, e.g. alkali metal free alumina ceramics
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/76—Crystal structural characteristics, e.g. symmetry
- C04B2235/762—Cubic symmetry, e.g. beta-SiC
- C04B2235/764—Garnet structure A3B2(CO4)3
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
- C04B2235/786—Micrometer sized grains, i.e. from 1 to 100 micron
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9646—Optical properties
- C04B2235/9653—Translucent or transparent ceramics other than alumina
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Compositions Of Oxide Ceramics (AREA)
- General Engineering & Computer Science (AREA)
- Ceramic Products (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
本发明的主题是透明陶瓷及其用途。所述透明陶瓷具有在2mm厚的抛光的玻璃上用波长为600nm的光测量的>75%的RIT和在>10至=<100微米,优选>10至50微米,更优选>10至20微米范围的平均粒度。所述透明陶瓷例如是Mg-Al-尖晶石、ALON、氧化铝、钇铝石榴石、氧化钇或氧化锆。
Description
本发明的主题是透明陶瓷、其制备方法及其用途。
本发明涉及高强度透明陶瓷,其包括所有的透明陶瓷材料,例如Mg-Al-尖晶石、AlON、钇铝石榴石、氧化钇、氧化锆等。特别令人感兴趣的是具有增加的机械负荷能力的材料,且在此特别是保护陶瓷,如Mg-Al-尖晶石、 、氧化铝等。
为了保护例如车辆如军用车辆或部分民用车辆免受射击而给它们装甲。装甲通常借助金属-或金属-陶瓷-体系进行。然而,这样的体系不能用于包含窗户,像侧窗玻璃、挡风玻璃等区域。给这些区域例如配备防弹玻璃。但是,众所周知,恰恰对穿甲武器,防弹玻璃具有比所述复合体系或金属装甲体系明显更低的弹道学效率。其结果是配备有防弹玻璃的窗户区域是车辆的薄弱处。足够的防护性能只能通过非常大的重量来实现,因此车辆的机动性和有效载重限值明显降低。
与防弹玻璃相比,透明陶瓷具有改进的保护性能。出于这个原因,相对早就已经在寻找防弹玻璃的替代方案。这些基本上是在陶瓷如尖晶石和中找到。与防弹玻璃相比,这些陶瓷具有改进的机械性能,如提高的强度和硬度。但是,与防弹玻璃相反,在已知陶瓷的情况中,难于生产几乎无缺陷的部件。在透明陶瓷的部件中,大都留有零星的较大的> 100μm的缺陷。这样的缺陷的实例尤其是由于在透明陶瓷的原料粉末中的孔造成的孔,以及颗粒残余物,压制缺陷,脱气(Entgasungen),有机夹杂物或诸如此类的。虽然这些缺陷不一定影响透明度的测量,但它们不利于视野因而是应避免的。夹杂物,如其在压制方法中是不能有效避免的,尤其是在作为透明陶瓷保护材料使用时减小了陶瓷材料的效用。此外另一效果是:
例如,在"International Journal of Impact Engineering",2002年5月27日,509-520中报道,HEL(Hugenostic弹性极限)对于作为弹道保护的陶瓷的有效性而言是决定性量值。此外发现孔隙率对HEL的强烈影响。较大的孔 - 在数量和具体尺寸方面 –使HEL减少并因此减小保护作用。
在"Ceramic Engineering and Science Proceedings",26:77,2005,123-130中描述了孔隙率是与损伤关系重大的,因为它被确定为材料流动的触发器并因此破坏陶瓷。
此外,已经表明,强度对于车辆中透明陶瓷的窗玻璃的安装而言是一个重要参数,因为由于机械应力,如石头的撞击或车辆的扭转,合适的强度是必要的。因为通常希望相对薄的陶瓷层,所以希望相应大的强度,以能够实现薄的窗玻璃。也就是说,对于使用而言,整个部件- 大都以单个砖的形式 - 的强度是非常重要的。因为在陶瓷部件中最大的缺陷是与失效关系重大的,所以小的个体标本上的高强度没有提供足够的信息。
高的四点弯曲强度是用以表征该部件的一个好的测量尺寸。为满足本发明的较高的强度要求,在四点弯曲试样中不允许存在大的结构缺陷,从而降低在较大的部件中存在相应缺陷的概率。为了满足最低要求,按照DIN EN843-1,在四点弯曲试样中应不存在>100μm的缺陷,更好不存在>20μm的缺陷。
在迄今的研发中一直试图实现具有提高的强度的部件。MER公司,Tucson, Arizona, USA,已经产生了具有约300MPa的四点弯曲强度的尖晶石。在大都借助LiF制备的热压部件中,所述孔具有有利于透明度的光滑表面,并因此不是光学上不利的。然而,借助显微分析可以检测到存在较大的孔,此外由于高的工艺温度造成的大的晶体同样具有降低强度的作用。最大四点弯曲强度为平均≤300MPa(MER数据)。根据EP 1557402 A2制备的具有粒度< 1μm的陶瓷似乎也具有降低强度的元素,因为在那里给出的200-250MPa的强度甚至低于热压部件的强度。尽管没有公开各夹杂物的大小数据,但这样的夹杂物造成了低强度,因为甚至在≥50μm的粒度下也可以测得更高的强度。
借助SPS(= Spark Plasma-Sintering(火花等离子烧结)),如在“Condition Optimization for Producing Transparent MgAl2O4 Spinel Polycrystal”; J. Am. Ceram. Soc; 92 (6) 1208-1216 (2009), Morita等中描述的,虽然可以实现400MPa的强度;然而,这里所描述的部件在光波长为600nm时具有<70%的RIT,因此,其不适合用作透明保护或类似的。也就是说,高强度迄今不能与必要的高的>75%的RIT相结合。
本发明改善了透明陶瓷在增加的机械应力下的应用可能性,并因此能够更有效地使用这些陶瓷,因为例如能够制造和使用更薄的部件,但所述部件由于其较小的断裂倾向能够满足具有较低强度的较厚部件的同样的功能。在用作防弹保护时,此优势尤为明显。
对于透明陶瓷的品质而言另一个重要的参数是在陶瓷中的散射损失。陶瓷中的散射损失由于陶瓷中的瑕疵引起。为保持陶瓷中的散射损失尽可能小,因此尽可能小的瑕疵发生率是必要的。只有以这种方式才能实现对于大量应用可能性,如光学透镜,防护眼镜,视孔玻璃,在磨损区域中的激光等而言合适的光学品质。在这些散射中心的数目过大或者通常直径过大的情况中,透明陶瓷的光学品质急剧降低。
例如,在透明保护窗玻璃或磨损防护窗玻璃的情况中,这造成驾驶员/装置操作员的混淆。也就是说,这里不利影响人体工程学。在透镜、激光或其它光学精密系统的情况中,将不利影响其性能和精度。因此,必须确保一定的光学品质。
这类瑕疵/散射中心的原因可能是由于化学杂质或由于工艺缺陷引起的第二相。
因此,本发明的目的在于实现结合了高透明度(RIT > 75%)和高的光学品质的具有高强度的透明陶瓷。
根据本发明,该目的通过权利要求1的特征得以实现。优选的本发明的实施方案和扩展方案在从属权利要求中表明。
令人惊讶地,所述作为本发明的基础的目的通过平均粒度在某一范围内变动的陶瓷得以实现。在此已证实,如果代替具有非常细的平均粒度的陶瓷,例如如果代替具有平均粒度在<1μm范围的陶瓷,提供具有高透明度(RIT>75%)和高的光学品质的具有平均粒度在>10至≤100μm范围的陶瓷,优选具有平均粒度在>10至50μm范围的陶瓷,特别优选具有平均粒度在>10至20μm范围的陶瓷,非常特别优选具有平均粒度在11至20μm范围的陶瓷,则可以令人惊讶地提高本发明范围内的陶瓷的工作能力。
根据本发明待使用的原料具有<2μm的平均初级颗粒尺寸d50,优选5至500nm,和> 99.5%,优选> 99.9%的纯度,即具有最大杂质<0.5%或<0.1%。
根据本发明,特别优选使用具有小的附聚倾向的原材料。
平均粒度根据线截取法按照DIN EN623来测定,RIT值在2mm厚的,抛光后的玻璃上用600nm波长的光测定。
在本发明范围内,高的光学品质通过根据下文描述的方法测定的瑕疵发生率的比例来表征。优选的根据本发明的陶瓷具有<10%的瑕疵发生率,特别优选的根据本发明的陶瓷具有<1%的瑕疵发生率。
透明陶瓷的另一重要方面是陶瓷必要的良好的可抛光性和可继续加工性的,因为由此显著影响很大比例的总成本。已经令人惊奇地发现,在本发明的具有平均粒度在>10至≤100μm范围的陶瓷中,特别是在本发明的具有平均粒度在>10至20μm范围的陶瓷中未能发现在具有平均粒度在<10μm范围的陶瓷中开始的显著的微粒硬化。从现有技术中已知的具有平均粒度在<10μm范围的陶瓷中显著开始的微粒硬化不仅使陶瓷的加工变得困难,而且此外也使断裂行为恶化。
这是尤其令人惊讶的,因为本发明陶瓷的硬度比现有技术中已知的具有较细的平均粒度的陶瓷小。
本发明的陶瓷的另一个优点是其特别好的弹道学工作能力,这已通过与细晶陶瓷(粒度<1μm)比较的射击试验发现。本发明的陶瓷的弹道学优点是特别令人惊奇的,因为其硬度比由现有技术中已知的非常细的陶瓷(例如EP1557402 A2,DE 10 2004004259)小,但断裂行为更好。但另一方面,本发明的陶瓷的硬度和断裂行为与已知的粗晶陶瓷(例如US 2004/0266605,US5001093,US4983555)相比更好。此外,尤其有利于多次射击(耐多次击打),即由本发明的陶瓷制成的透明弹道目标的三角射击。
在根据本发明的>10至≤100μm范围内的平均粒径,特别是在根据本发明的>10至50μm范围内的平均粒径此外能够实现最佳加工,比细晶材料(硬度比细晶材料小)更易切削(例如水射流),相对于粗晶材料简化的研磨、抛光(脱落的晶体较小)。在可能的自由变形曲面的后续设计中,该简化的加工允许重要的自由度。这尤其在民用防护车辆的弯曲窗玻璃的设计中是特别令人感兴趣的。
根据本发明的陶瓷的另一优点在于显著更有利的生产成本,因为能够使用较粗并因此价格更便宜的粉末(平均(最终-)粒度在>10至≤100μm的范围),最佳的硬加工和更有利的生产方法是可能的。因为在一般的经济的生产过程中,原材料在生产成本中明显占最大比例,所以恰恰通过使用较粗的原料就能生产的显著更便宜的产品。
迄今,恰恰是由现有技术已知的透明陶瓷的价格阻止了在弹道学中的更大范围的市场准入。所使用的热压、必需通过其他途径制造的细纳米粉或极其昂贵的抛光剂造成了迄今极其高的价格。
因此,本发明的主题具体是:
· 透明陶瓷,其具有在2 mm厚的抛光的玻璃上用波长为600 nm的光测量>75%的RIT和在> 10至≤100 μm范围的平均粒度,优选具有平均粒度在>10至50μm范围的透明陶瓷,特别优选具有平均粒度在>10至20μm范围的透明陶瓷,非常特别优选具有平均粒度在11至20μm范围的透明陶瓷;
优选的是如上所述的透明陶瓷,其
· 具有高的光学品质
· 具有 <10%的瑕疵发生率,特别优选< 1的瑕疵发生率;
· 具有第二相,其尺寸最大< 2000 μm,优选 < 200 μm;
· 包含下述物质的氧化物的一种:锆、铝、镁、钇、锌、锡、钙、钛、镓、铟、铪、钪、铈、铕、钡或其组合;
· 包含Mg-Al-尖晶石、、氧化铝、钇铝石榴石、氧化钇、氧化锆;
· 包含ALON;
· 是尖晶石陶瓷。
本发明的陶瓷例如可用于弹道学中。
下面借助实施例解释本发明。
实施例1:
将尖晶石粉末(MgAl2O3)加工成50质量%的浆料。随后借助偏心螺杆泵将该稀粘的浆液喷入流化床造粒装置中。作为粉末床,事先将纯粉末置入该装置中。通过缓慢而连续的浆料输送,所述材料被缓慢连续地造粒。如此设定压力条件和空气供给,以至于生产在d10 = 100 μm和d90 = 300 μm的尺寸范围的颗粒。如此制得的颗粒是实心颗粒,其绝不会具有如空心球结构或圆环形状的不均匀性。然后将该颗粒在160MPa下单轴向压制成具有50毫米×50毫米尺寸的板,由于其均匀性可将其在1500℃致密烧结。此后,同样在1500℃和2000bar下进行HIP-方法。在HIP-过程之后,类似于DIN EN 623-2根据阿基米德方法测定,得到3.575g/cm3测得的密度。这代表> 99.9 % 的密度。由该高均匀密度得到83%的RIT值 - 在制造的板内具有0.2 %的波动。存在的瑕疵比例≤ 0.5 % 。在热蚀刻抛光样品后,根据线-截取-法按照DIN EN623确定的陶瓷的平均粒度为12μm+/- 0.5μm。
将如此制得的本发明陶瓷通过下述方法进一步进行瑕疵分析,并根据所希望的规格相应分离。
瑕疵分析方法:
在制备透明陶瓷时显示出,大多数样品中没有产生明净的试样,而是所有样品均掺以几μm至数百μm大小范围的瑕疵。出于这个原因,有必要分析和量化,因为它们妨碍之后由本发明的陶瓷制成的部件的光学外观。此外显示出,不同的样品掺有不同程度的瑕疵。这样的例子示于图1中。图1显示了一张得自纯粉末的冷等静压压制试样的照片。
在进一步观察时,一些瑕疵显得更像裂纹或球形或较大的楔形物。这种缺陷的原因可能是化学杂质、压制缺陷或其它压制中的缺陷。因此,在这些区域中由于散射出现宏观瑕疵。因此似乎给出了生坯中的残余物、杂质与之后的瑕疵之间的直接关系。
下面描述的用于瑕疵分析的方法提供了对瑕疵尺寸分布、瑕疵发生率和样品中瑕疵总和的信息。为此,在光学显微镜中聚焦于样品中心和样品表面并拍摄照片。该照片用自动图像处理分成白色和黑色区域,以至于可以识别瑕疵和透明的区域之间明显的视觉差异。显微镜分析后(左)和图像处理后(右)的典型图像示于图2中。可使用6.3倍放大倍率和1280×1024像素的分辨率。
随后借助图像处理软件和Excel程序对该图像的瑕疵发生率分布和面积(夹杂物作为总面积的比例EF)(图3)进行评价。平均夹杂物尺寸为ED50。在图3中,其等价圆直径以μm分类在x轴上给出,而表面重现性以%在Y轴上给出。d50值存在于281.14μm处,最大瑕疵具有484μm的等价圆直径和0.44%的面积比例。轴因子为1.5。
评价的精确度通过分辨率(标准的1280 * 1024像素)以及误差大小和放大率确定。
对于ED50,精确度为 。在最常用的63倍放大倍率的情况下,对于ED50而言得到±0.9的精确度。对于面积比率EF +-2.72μm2或+ - 7.6*10^-5%。因为该方法发现,当局部瑕疵由于图像处理而消失时,也能确保结果的高再现性。
Claims (11)
1.透明陶瓷,其特征在于,所述透明陶瓷具有在2 mm厚的抛光的玻璃上用波长为600 nm的光测量的>75%的RIT和在> 10至≤100 μm范围的平均粒度。
2.透明陶瓷,其特征在于,所述透明陶瓷具有在2 mm厚的抛光的玻璃上用波长为600 nm的光测量的>75%的RIT,在> 10至≤100 μm范围的平均粒度和高的光学品质。
3.根据权利要求1或2所述的透明陶瓷,其特征在于,所述透明陶瓷具有在 >10至 50 μm 范围的平均粒度。
4.根据权利要求1或2所述的透明陶瓷,其特征在于,所述透明陶瓷具有在> 10至 20 μm范围的平均粒度。
5.根据权利要求 1至4的一项或多项所述的透明陶瓷,其特征在于,所述透明陶瓷具有< 10%的瑕疵发生率,特别优选< 1 %的瑕疵发生率。
6.根据权利要求2至5的一项或多项所述的透明陶瓷,其特征在于,所述透明陶瓷具有第二相,所述第二相的大小为最大< 2000 μm,优选 < 200 μm。
7.根据权利要求 1至6的一项或多项所述的透明陶瓷,其特征在于,所述透明陶瓷包含下述物质的氧化物的一种:锆、铝、镁、钇、锌、锡、钙、钛、镓、铟、铪、钪、铈、铕、钡或其组合。
8.根据权利要求1至 6的一项或多项所述的透明陶瓷,其特征在于,所述透明陶瓷包含Mg-Al-尖晶石、 、氧化铝、钇铝石榴石、氧化钇或氧化锆。
9.根据权利要求1至6的一项或多项所述的透明陶瓷,其特征在于,所述透明陶瓷包含ALON。
10.根据权利要求 1至 6的一项或多项所述的透明陶瓷,其特征在于,所述透明陶瓷是尖晶石陶瓷。
11.根据权利要求 1至 10之一的透明陶瓷在弹道学中的用途。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102011085868.7 | 2011-11-07 | ||
DE102011085868 | 2011-11-07 | ||
PCT/EP2012/072055 WO2013068418A1 (de) | 2011-11-07 | 2012-11-07 | Transparente keramik |
Publications (1)
Publication Number | Publication Date |
---|---|
CN104024179A true CN104024179A (zh) | 2014-09-03 |
Family
ID=47148806
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201280054455.0A Pending CN104024179A (zh) | 2011-11-07 | 2012-11-07 | 透明陶瓷 |
Country Status (12)
Country | Link |
---|---|
US (1) | US20140360345A1 (zh) |
EP (1) | EP2776379A1 (zh) |
JP (1) | JP6195838B2 (zh) |
KR (1) | KR20140103111A (zh) |
CN (1) | CN104024179A (zh) |
AR (1) | AR088684A1 (zh) |
BR (1) | BR112014010888A8 (zh) |
DE (1) | DE102012220257A1 (zh) |
IL (1) | IL232465A0 (zh) |
IN (1) | IN2014CN04116A (zh) |
RU (1) | RU2014123066A (zh) |
WO (1) | WO2013068418A1 (zh) |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015501775A (ja) * | 2011-11-10 | 2015-01-19 | セラムテック−イーテック ゲゼルシャフト ミット ベシュレンクテル ハフツングCeramTec−Etec GmbH | 流動層造粒による透明セラミック物体の製造法 |
US10676400B2 (en) | 2014-05-21 | 2020-06-09 | Ceramtec-Etec Gmbh | Ceramics wringing |
EP2949633B1 (de) | 2014-05-27 | 2019-04-24 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Transparente Spinellkeramiken und Verfahren zu ihrer Herstellung |
US9309156B2 (en) | 2014-05-27 | 2016-04-12 | Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. | Transparent spinel ceramics and method for the production thereof |
DE102014210071A1 (de) | 2014-05-27 | 2015-12-03 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Transparente Spinellkeramiken und Verfahren zu ihrer Herstellung |
WO2015181066A1 (de) | 2014-05-27 | 2015-12-03 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Transparente spinellkeramiken und verfahren zu ihrer herstellung |
KR20170015278A (ko) * | 2014-05-30 | 2017-02-08 | 스미토모덴키고교가부시키가이샤 | 액정 터치 패널 보호판 |
US9287106B1 (en) | 2014-11-10 | 2016-03-15 | Corning Incorporated | Translucent alumina filaments and tape cast methods for making |
CN115351886A (zh) | 2015-10-16 | 2022-11-18 | 圣戈本陶瓷及塑料股份有限公司 | 具有复杂几何形状的透明陶瓷和其制造方法 |
WO2018013387A1 (en) * | 2016-07-13 | 2018-01-18 | Tosoh Smd, Inc. | Magnesium oxide sputtering target and method of making same |
DE102016009730A1 (de) * | 2016-07-28 | 2018-02-01 | Forschungszentrum Jülich GmbH | Verfahren zur Verstärkung von transparenten Keramiken sowie Keramik |
WO2018174814A1 (en) * | 2017-03-23 | 2018-09-27 | Dso National Laboratories | A protective material |
US12024468B2 (en) | 2018-12-14 | 2024-07-02 | Fraunhofer-Gesellschaft Zue Förderung Der Angewandten Forschung E.V. | Process for producing thin transparent ceramic parts and thin transparent ceramic parts |
CN113185301B (zh) * | 2021-04-23 | 2022-11-18 | 北京科技大学 | 一种AlON透明陶瓷的快速制备方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050164867A1 (en) * | 2004-01-23 | 2005-07-28 | Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. | Transparent polycrystalline sintered ceramic of cubic crystal structure |
DE102010007359A1 (de) * | 2009-08-31 | 2011-03-17 | Ceramtec-Etec Gmbh | Hochfeste transparente Keramik |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4285732A (en) * | 1980-03-11 | 1981-08-25 | General Electric Company | Alumina ceramic |
US4686070A (en) * | 1981-08-31 | 1987-08-11 | Raytheon Company | Method of producing aluminum oxynitride having improved optical characteristics |
US5001093A (en) * | 1987-05-06 | 1991-03-19 | Coors Porcelain Company | Transparent polycrystalline body with high ultraviolet transmittance |
US4983555A (en) | 1987-05-06 | 1991-01-08 | Coors Porcelain Company | Application of transparent polycrystalline body with high ultraviolet transmittance |
JPH07115917B2 (ja) * | 1988-01-13 | 1995-12-13 | 新光電気工業株式会社 | ムライトセラミック組成物 |
JPH0323269A (ja) * | 1989-06-16 | 1991-01-31 | Sumitomo Electric Ind Ltd | 透光性酸窒化アルミニウム焼結体及びその製造方法 |
JP2001064075A (ja) * | 1999-08-30 | 2001-03-13 | Sumitomo Chem Co Ltd | 透光性アルミナ焼結体およびその製造方法 |
US8211356B1 (en) * | 2000-07-18 | 2012-07-03 | Surmet Corporation | Method of making aluminum oxynitride |
US20040266605A1 (en) | 2003-06-24 | 2004-12-30 | Villalobos Guillermo R. | Spinel and process for making same |
JP2006273679A (ja) * | 2005-03-30 | 2006-10-12 | Sumitomo Electric Ind Ltd | スピネル焼結体、光透過窓および光透過レンズ |
JP5000934B2 (ja) * | 2006-06-22 | 2012-08-15 | 神島化学工業株式会社 | 透光性希土類ガリウムガーネット焼結体及びその製造方法と光学デバイス |
WO2008090909A1 (ja) * | 2007-01-23 | 2008-07-31 | World Lab. Co., Ltd. | 透明スピネルセラミックス及びその製造方法ならびにその透明スピネルセラミックスを用いた光学材料 |
US20080283522A1 (en) * | 2007-05-14 | 2008-11-20 | Shuyl Qin | Translucent polycrystalline alumina ceramic |
EP2305621B1 (en) * | 2009-09-09 | 2015-04-22 | NGK Insulators, Ltd. | Translucent polycrystalline sintered body, method for producing the same, and arc tube for high-intensity discharge lamp |
KR20120098118A (ko) * | 2011-02-28 | 2012-09-05 | 영남대학교 산학협력단 | 투명도가 향상된 다결정 산질화알루미늄의 제조방법 |
-
2012
- 2012-11-07 EP EP12783991.8A patent/EP2776379A1/de not_active Ceased
- 2012-11-07 DE DE102012220257A patent/DE102012220257A1/de not_active Withdrawn
- 2012-11-07 BR BR112014010888A patent/BR112014010888A8/pt not_active IP Right Cessation
- 2012-11-07 IN IN4116CHN2014 patent/IN2014CN04116A/en unknown
- 2012-11-07 AR ARP120104185A patent/AR088684A1/es unknown
- 2012-11-07 KR KR1020147015370A patent/KR20140103111A/ko not_active Application Discontinuation
- 2012-11-07 RU RU2014123066/03A patent/RU2014123066A/ru not_active Application Discontinuation
- 2012-11-07 WO PCT/EP2012/072055 patent/WO2013068418A1/de active Application Filing
- 2012-11-07 CN CN201280054455.0A patent/CN104024179A/zh active Pending
- 2012-11-07 JP JP2014540441A patent/JP6195838B2/ja not_active Expired - Fee Related
- 2012-11-07 US US14/355,245 patent/US20140360345A1/en not_active Abandoned
-
2014
- 2014-05-05 IL IL232465A patent/IL232465A0/en unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050164867A1 (en) * | 2004-01-23 | 2005-07-28 | Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. | Transparent polycrystalline sintered ceramic of cubic crystal structure |
DE102010007359A1 (de) * | 2009-08-31 | 2011-03-17 | Ceramtec-Etec Gmbh | Hochfeste transparente Keramik |
Non-Patent Citations (1)
Title |
---|
JUN ZHOU ET.AL.: "Optical properties of Er,Yb co-doped YAG transparent ceramics", 《CERAMICS INTERNATIONAL》, vol. 37, no. 2, 1 March 2011 (2011-03-01), pages 513 - 519, XP027558927 * |
Also Published As
Publication number | Publication date |
---|---|
WO2013068418A1 (de) | 2013-05-16 |
DE102012220257A1 (de) | 2013-05-08 |
BR112014010888A8 (pt) | 2017-06-20 |
BR112014010888A2 (pt) | 2017-06-13 |
JP2014532615A (ja) | 2014-12-08 |
EP2776379A1 (de) | 2014-09-17 |
IN2014CN04116A (zh) | 2015-07-10 |
US20140360345A1 (en) | 2014-12-11 |
IL232465A0 (en) | 2014-06-30 |
AR088684A1 (es) | 2014-06-25 |
KR20140103111A (ko) | 2014-08-25 |
JP6195838B2 (ja) | 2017-09-13 |
RU2014123066A (ru) | 2015-12-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104024179A (zh) | 透明陶瓷 | |
Benitez et al. | Transparent ceramic and glass-ceramic materials for armor applications | |
Goldstein et al. | Transparent ceramics at 50: progress made and further prospects | |
KR101123553B1 (ko) | 스파크 플러그 및 스파크 플러그의 제조 방법 | |
CN106342081B (zh) | 一种氮氧化铝透明陶瓷的固相制备方法 | |
US8093791B2 (en) | Spark plug having particular insulator | |
US7148480B2 (en) | Polycrystalline optical window materials from nanoceramics | |
EP2413441A1 (en) | Spark plug | |
WO2007001387A9 (en) | Polycrystalline alumina articles and methods of manufacture | |
US20170166484A1 (en) | Method for producing transparent alumina sintered body | |
EP2864731B1 (en) | Ceramic compositions comprising alumina | |
CN110475760A (zh) | 致密烧结产品 | |
US8313725B2 (en) | Ready-to-sinter spinel nanomixture and method for preparing same | |
Li et al. | Passive application/window, dome, and armor | |
Parish et al. | Aerodynamic IR domes of polycrystalline alumina | |
Sutorik et al. | Development of transparent ceramic spinel (MgAl2O4) for armor applications | |
Dixit et al. | Investigation of mechanical properties based on the particle size of alumina ceramics prepared by circulatory bead milling | |
Schlup | Processing Aluminum Oxide for the Control of Microstructural Texture and Optical Properties | |
DE102010007359A1 (de) | Hochfeste transparente Keramik | |
TWI778688B (zh) | 陶瓷構造體及靜電偏向器 | |
Luo et al. | Magnesium aluminate spinel transparent ceramics with high optical and mechanical performance by Y3Al5O12 sintering additive | |
Sanghera et al. | Transparent ceramics for high-power solid-state lasers | |
Mota et al. | Microstructural evaluation of alumina-niobium and alumina-niobium-zircon ceramics for ballistic application | |
Yoshida | Electric Field/Current-Assisted Sintering of Optical Ceramics | |
WO2018174814A1 (en) | A protective material |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140903 |
|
RJ01 | Rejection of invention patent application after publication |