TWI631090B - Near infrared absorption material and method for fabricating the same - Google Patents
Near infrared absorption material and method for fabricating the same Download PDFInfo
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Abstract
本發明提供一種近紅外光阻隔材料的製造方法，包含：提供一含碳酸鹽觸媒，提供一羥肟酸螯合劑，提供一含鎢前驅物及提供一鹼金族金屬鹽；混合該含鎢前驅物、該羥肟酸螯合劑、該鹼金族金屬鹽、與該含碳酸鹽觸媒，形成一混合物；以及對該混合物在約600℃至800℃下以還原氣體進行反應燒結，以形成一鹼金族摻雜之鎢青銅。本發明又提供一種近紅外線阻隔材料與其製造方法。該近紅外光阻隔材料包含：一鎢青銅複合物，具有化學式表示如下：CMxWyOz，其中0.34x/y0.45與2.50z/y3.0，且M為摻雜物為鈉(Na)、鉀(K)、銣(Rb)、或銫(Cs)，C為碳、W為鎢、O為氧，其中，該鎢青銅複合物由一焦綠石相鎢青銅(pyrochlore)、以及一六方晶相鎢青銅(hexagonal tungsten bronze、HTB)所複合組成。 The invention provides a method for manufacturing a near-infrared light blocking material, comprising: providing a carbonate-containing catalyst, providing a hydroxamic acid chelating agent, providing a tungsten-containing precursor and providing an alkali metal group metal salt; and mixing the tungsten-containing metal salt a precursor, the hydroxamic acid chelating agent, the alkali metal group metal salt, and the carbonate-containing catalyst form a mixture; and the mixture is subjected to reaction sintering at a temperature of about 600 ° C to 800 ° C to form a reducing gas to form An alkali gold doped tungsten bronze. The invention further provides a near infrared ray blocking material and a method of manufacturing the same. The near-infrared light blocking material comprises: a tungsten bronze composite having the chemical formula as follows: CM x W y O z , wherein 0.34 x/y 0.45 and 2.50 z/y 3.0, and M is a dopant of sodium (Na), potassium (K), strontium (Rb), or strontium (Cs), C is carbon, W is tungsten, and O is oxygen, wherein the tungsten bronze composite is composed of A pyrochlore phase consists of pyrochlore and hexagonal tungsten bronze (HTB).
Description
本發明是關於一種近紅外線阻隔材料與其製造方法，尤指一種晶體微量區域還原反應的鹼金族金屬摻雜鎢青銅。 The invention relates to a near-infrared ray blocking material and a manufacturing method thereof, in particular to an alkali gold group metal doped tungsten bronze which is reduced in a crystal region.
近年來由於環境保護、節能減碳的意識日益增長，讓許多有助於減少能源消耗的各種技術得以快速發展，其中對於建築物開口部可阻隔輻射熱的產品開發更是重要，如果使用適當的隔熱窗材可以有效降低由窗戶部分進入建築物的熱輻射達20%以上，所以，在透明隔熱材料的使用上已經是節能省電的一級戰場。而金屬氧化物的物性，具有隔熱效果，已廣泛做為阻隔紅外線的材料。 In recent years, due to the growing awareness of environmental protection, energy conservation and carbon reduction, many technologies that help reduce energy consumption have been rapidly developed, and it is even more important for the development of products that block radiant heat in the opening of buildings, if appropriate partitions are used. The hot window material can effectively reduce the heat radiation entering the building by the window part by more than 20%. Therefore, it is already the first-class battlefield for energy saving and power saving in the use of transparent heat insulating material. The physical properties of metal oxides have a heat insulating effect and have been widely used as materials for blocking infrared rays.
因此，開發更能阻隔紅外線之透明隔熱材料是時勢所趨。然而，目前的隔熱材料就隔熱效能上來比較已經由以往的銻摻雜氧化錫(ATO)、六硼化鑭(LaB6)等材料系統進步到鹼金族金屬鹽摻雜型氧化鎢。 Therefore, it is a constant trend to develop transparent insulation materials that are more resistant to infrared rays. However, the current thermal insulation performance of the thermal insulation material has been improved from the conventional bismuth doped tin oxide (ATO), lanthanum hexaboride (LaB6) and other material systems to the alkali gold metal salt doped tungsten oxide.
而在鹼金族金屬鹽摻雜型氧化鎢的領域中又 以鈉元素或銫元素的摻雜最為普遍，但這兩種類型的摻雜型或共摻雜型氧化鎢都有材料穩定性不佳、長時間使用後特性衰退的問題。追究其原因，歸因於氧化鎢製造時的摻雜比例失調、晶體晶相穩定度差、與還原製程中的整體還原均勻性不佳等三個主因。 And in the field of alkali metal group metal salt doped tungsten oxide Doping with sodium or lanthanum is most common, but both types of doped or co-doped tungsten oxide have poor material stability and degraded characteristics after prolonged use. The reason for this is attributed to three main reasons, such as the mismatch of doping ratio in the manufacture of tungsten oxide, the poor stability of crystal phase, and the poor overall uniformity of reduction in the reduction process.
而目前有許多專利利用元素共摻雜方式來使主要銫或鈉摻雜元素的穩定性提高，但是額外摻雜元素容易在在粉體燒結時產生其他不相容的晶相，導致晶體的晶格產生扭曲而使材料穩定性變差，在耐候性(紫外光曝曬測試)上產生近紅外光阻隔效能降低的副作用。另外，也有專利使用乾式製程將碳系材料與氧化鎢(銫鎢青銅)混合，利用碳系材料吸收陽光的特性強化氧化鎢吸收陽光的性能，但此種類型的材料組合並沒有改善鹼金族金屬摻雜氧化鎢在元素摻雜比例失衡以及整體材料還原不均勻，所造成光學穩定性變化的問題。 At present, there are many patents that use element co-doping to improve the stability of the main antimony or sodium doping elements, but the additional doping elements tend to produce other incompatible crystal phases during the sintering of the powder, resulting in crystal crystals. The lattice is distorted to deteriorate the material stability, and the side effect of reducing the near-infrared light blocking performance is produced on the weather resistance (ultraviolet light exposure test). In addition, there are patents that use a dry process to mix carbon-based materials with tungsten oxide (tungsten-tungsten bronze). The use of carbon-based materials to absorb sunlight enhances the performance of tungsten oxide to absorb sunlight. However, this type of material combination does not improve the alkali metal family. The problem of the optical stability of the metal-doped tungsten oxide is unbalanced in the element doping ratio and the overall material reduction is not uniform.
本發明之實施例提供一種近紅外光阻隔材料的製造方法，包含：提供一含鎢前驅物；提供一羥肟酸金屬螯合劑；提供一鹼金族金屬鹽；提供一含碳酸鹽觸媒；混合該鹼金族金屬鹽、該含碳酸根金屬鹽、該含鎢前驅物與該羥肟酸金屬螯合劑，形成一混合物，利用羥肟酸金屬螯合劑對於鎢離子的螯合作用，提高鎢與鹼金族金屬對氧的配位混合率，使金屬離子摻雜比例獲得較佳控制；以及， 對該混合物進行一加熱燒結製程並使用還原氣氛，藉由高溫的加熱燒結與高反應性還原氣體輔助製程誘發混合包覆在鎢青銅前驅物表面的碳酸根離子裂解成二氧化碳、與一氧化碳等微區還原氣氛元素，均質化每個鎢青銅晶體周圍的還原氣氛，使摻雜金屬的比例均質化，得到上述高均質化的近紅外光阻隔材料。 An embodiment of the present invention provides a method for producing a near-infrared light-blocking material, comprising: providing a tungsten-containing precursor; providing a metal hydroxy chelating agent; providing an alkali metal group metal salt; and providing a carbonate-containing catalyst; Mixing the alkali metal group metal salt, the metal carbonate-containing metal salt, the tungsten-containing precursor and the metal hydroxy citrate chelating agent to form a mixture, and enhancing the chelation of tungsten ions by using a metal chelating agent of hydroxamic acid The coordination mixing ratio with the alkali gold metal to oxygen makes the metal ion doping ratio better controlled; and, The mixture is subjected to a heating and sintering process and a reducing atmosphere is used, and the carbonate ions of the surface of the tungsten bronze precursor are mixed and cleaved into carbon dioxide, carbon monoxide and the like by high temperature heating sintering and high reactivity reducing gas assisted process. The atmosphere element is reduced, the reducing atmosphere around each tungsten bronze crystal is homogenized, and the proportion of the doping metal is homogenized to obtain the above-mentioned highly homogenized near-infrared light blocking material.
本發明是提供一種近紅外光阻隔材料，包含：一含碳鎢青銅複合物，具有化學式表示如下：CMxWyOz，其中0.34x/y0.45、2.50z/y3.0，且M為摻雜物為鈉(Na)、鉀(K)、銣(Rb)、或銫(Cs)，C為碳、W為鎢、O為氧。其中，該含碳之鎢青銅複合物由一焦綠石相鎢青銅(pyrochlore)、以及一六方晶相鎢青銅(hexagonal tungsten bronze、HTB)所複合組成。該近紅外光阻隔材料可應用於高耐候性隔熱結構，符合高透光率、及高隔熱性的要求。 The invention provides a near-infrared light blocking material comprising: a carbon-containing tungsten bronze composite having the chemical formula represented as follows: CM x W y O z , wherein 0.34 x/y 0.45, 2.50 z/y 3.0, and M is a dopant of sodium (Na), potassium (K), ruthenium (Rb), or cesium (Cs), C is carbon, W is tungsten, and O is oxygen. The carbon-containing tungsten bronze composite is composed of a pyrochlore phase pyrochlore and a hexagonal tungsten bronze (HTB). The near-infrared light blocking material can be applied to a high weathering heat insulating structure, and meets the requirements of high light transmittance and high heat insulation.
第1圖為本發明實施例中所述的含碳之鎢青銅複合物之UV-VIS-IR光譜圖。 Fig. 1 is a UV-VIS-IR spectrum of the carbon-containing tungsten bronze composite according to the embodiment of the present invention.
第2圖為比較本發明比較例1在進行紫外光曝曬測試前後之UV-VIS-IR光譜圖。 Fig. 2 is a comparison of the UV-VIS-IR spectrum of Comparative Example 1 of the present invention before and after the ultraviolet light exposure test.
第3圖為本發明實施例3之具有焦綠石相與六方晶相複合之XRD光譜圖。 Fig. 3 is a view showing an XRD spectrum of a composite having a pyrochlore phase and a hexagonal phase in Example 3 of the present invention.
第4圖為比較本發明實施例3在進行紫外光曝曬測試前後之UV-VIS-IR光譜圖。 Figure 4 is a comparison of UV-VIS-IR spectra of Example 3 of the present invention before and after the UV exposure test.
本發明之實施例是提供一近紅外光阻隔材料與製程方法，是包含鎢青銅複合物。該鎢青銅複合物是由焦綠石相(pyrochlore)鎢青銅、以及六方晶相鎢青銅所複合組成。 Embodiments of the present invention provide a near-infrared light blocking material and process method comprising a tungsten bronze composite. The tungsten bronze composite is composed of pyrochlore tungsten bronze and hexagonal phase tungsten bronze.
根據本發明之實施例，本發明是提供一種近紅外光阻隔材料。該近紅外光阻隔材料包含：一含碳之鎢青銅複合物，具有化學式表示如下：CMxWyOz，其中0.34x/y0.45、2.50z/y3.0，且M為摻雜物為鈉(Na)、鉀(K)、銣(Rb)、或銫(Cs)，C為碳、W為鎢、O為氧。其中，該含碳之鎢青銅複合物由一焦綠石相鎢青銅(pyrochlore)、以及一六方晶相鎢青銅(hexagonal tungsten bronze、HTB)所複合組成。 According to an embodiment of the present invention, the present invention provides a near-infrared light blocking material. The near-infrared light blocking material comprises: a carbon-containing tungsten bronze composite having the chemical formula as follows: CM x W y O z , wherein 0.34 x/y 0.45, 2.50 z/y 3.0, and M is a dopant of sodium (Na), potassium (K), ruthenium (Rb), or cesium (Cs), C is carbon, W is tungsten, and O is oxygen. The carbon-containing tungsten bronze composite is composed of a pyrochlore phase pyrochlore and a hexagonal tungsten bronze (HTB).
根據本發明之實施例，當該含碳之鎢青銅複合物符合上述化學式組成時，可使得該近紅外光阻隔材料吸收85%以上的紅外光(780nm~2500nm)，且能讓大部分的可見光(400nm~780nm)穿透(平均可見光穿透率約70%以上)，如第1圖所示。 According to an embodiment of the present invention, when the carbon-containing tungsten bronze composite conforms to the chemical composition, the near-infrared light blocking material can absorb more than 85% of infrared light (780 nm to 2500 nm) and can make most of the visible light (400nm ~ 780nm) penetration (average visible light transmittance of about 70% or more), as shown in Figure 1.
根據本發明實施例，本發明亦提供一種近紅外光阻隔材料的製造方法，用以製備上述近紅外光阻隔材 料。該近紅外光阻隔材料的製造方法包括，提供一含鎢前驅物，例如鎢酸(tungstic acid)、矽化鎢(tungsten silicide)、鹼金族鎢酸鹽(alkali metal tungstate)、正鎢酸銨(ammonium orthotungstate)、偏鎢酸銨(ammonium metatungstate)、仲鎢酸銨(ammonium paratungstate)、硫化鎢(tungsten sulfide)、氯氧鎢(tungsten oxychloride)、烷氧基鎢(tungsten alkoxide)、六氯化鎢(tungsten hexachloride)、碳化鎢(tungsten carbide)、碳氧化鎢(tungsten oxycarbide)、或上述之組合。接著，提供一羥肟酸螯合劑，例如：水楊基羥肟酸(salicyl hydroxamic acid)、苯甲羥肟酸(benzoyl hydroxamic acid)、或烷基羥肟酸(alkyl hydroxamic acid)。 接著，提供一鹼金族金屬鹽及一碳酸鹽觸媒。接著，將該含鎢前驅物先與羥肟酸螯合劑混合後，再與鹼金族金屬鹽及碳酸鹽觸媒混合，形成一混合物。最後，對該混合物進行一加熱燒結製程，得到本發明所述之近紅外光阻隔材料。其中，該鹼金族金屬鹽是鈉金屬鹽、鉀金屬鹽、銣金屬鹽、或銫金屬鹽，例如硫酸鈉、碳酸鈉、氯化鈉、硫酸鉀、碳酸鉀、氯化鉀、硫酸銣、碳酸銣、氯化銣、硫酸銫、碳酸銫、氯化銫或上述之組合。 According to an embodiment of the present invention, the present invention also provides a method for manufacturing a near-infrared light blocking material, which is used for preparing the above-mentioned near-infrared light blocking material. material. The method for fabricating the near-infrared light-blocking material comprises providing a tungsten-containing precursor such as tungstic acid, tungsten silicide, alkali metal tungstate, orthotungstic acid ( Ammonium orthotungstate), ammonium metatungstate, ammonium paratungstate, tungsten sulfide, tungsten tungsten oxychloride, tungsten alkoxide, tungsten hexachloride ), tungsten carbide, tungsten oxide (tungsten oxycarbide), or a combination thereof. Next, a hydroxamic acid chelating agent such as salicyl hydroxamic acid, benzoyl hydroxamic acid, or alkyl hydroxamic acid is provided. Next, an alkali metal group metal salt and a monocarbonate catalyst are provided. Next, the tungsten-containing precursor is first mixed with a hydroxamic acid chelating agent, and then mixed with an alkali metal group metal salt and a carbonate catalyst to form a mixture. Finally, the mixture is subjected to a heat sintering process to obtain a near-infrared light blocking material according to the present invention. Wherein the alkali metal salt is a sodium metal salt, a potassium metal salt, a barium metal salt or a barium metal salt, such as sodium sulfate, sodium carbonate, sodium chloride, potassium sulfate, potassium carbonate, potassium chloride, barium sulfate, Barium carbonate, barium chloride, barium sulfate, barium carbonate, barium chloride or a combination thereof.
為得到上述具有特定化學結構以及特定晶相比例的近紅外光阻隔材料，該含鎢前驅物對該羥肟酸螯合劑的重量比例約介於30及25之間，該含鎢前驅物對該鹼金 族金屬鹽的重量比例約介於6及1.5之間，且該鹼金族金屬鹽對該碳酸鹽觸媒的重量比例約介於2.5及1之間。此外，對該混合物所進行的加熱製燒結程在溫度超過攝氏250度時，開始導入還原氣體，還原氣體的種類包含：90%氬氣與10%氫氣，或80%氬氣與20%氫氣，或90%氮氣與10%氫氣，或80%氮氣與20%氫氣，一直維持還原氣氛至攝氏700度至加熱還原製程結束，加熱還原時間約為8小時。值得注意的是，當加熱還原的反應時間不足8小時或超過12小時，會嚴重影響鎢青銅之M金屬元素摻雜量、以及晶型的轉換。舉例來說，當M金屬元素為銫(Cs)時，當加熱還原反應時間不夠時(不足8小時)，易使得摻雜銫的鎢青銅產生在氧化銫、單斜晶氧化鎢與六方晶相的銫鎢青銅，而不易獲得摻雜完整的焦綠石與六方晶複合的銫鎢青銅；舉例來說，當M金屬元素為銫(Cs)時，當加熱還原反應時間超時(超過12小時)，易使得摻雜銫的鎢青銅於焦綠石與六方晶複合晶相不穩定存在，而往六方晶相發展並且產生大量的紫鎢。值得注意的是，當含鎢前驅物對該羥肟酸螯合劑的重量比例約介於30及25之間，低於此比例(例如：含鎢前驅物對該羥肟酸螯合劑的重量比例小於25)會使金屬鎢形成，高於此比例對於穩定鎢及金屬離子對氧的配位效果不佳，並且使用羥肟酸螯合劑會在完成鎢青銅晶體後殘留微量碳元素於粉體之中。 In order to obtain the above-mentioned near-infrared light-blocking material having a specific chemical structure and a specific crystal phase ratio, the weight ratio of the tungsten-containing precursor to the hydroxamic acid chelating agent is between about 30 and 25, and the tungsten-containing precursor is Alkali gold The weight ratio of the metal salt of the group is between about 6 and 1.5, and the weight ratio of the alkali metal salt to the carbonate catalyst is between about 2.5 and 1. In addition, the heating process for the mixture begins to introduce a reducing gas at a temperature exceeding 250 degrees Celsius, and the reducing gas species include: 90% argon and 10% hydrogen, or 80% argon and 20% hydrogen, Or 90% nitrogen and 10% hydrogen, or 80% nitrogen and 20% hydrogen, maintaining the reducing atmosphere until 700 degrees Celsius until the end of the heating reduction process, the heating reduction time is about 8 hours. It is worth noting that when the reaction time of the heating reduction is less than 8 hours or more than 12 hours, the doping amount of the M metal element of the tungsten bronze and the conversion of the crystal form are seriously affected. For example, when the M metal element is lanthanum (Cs), when the heating reduction reaction time is insufficient (less than 8 hours), it is easy to cause yttrium-doped tungsten bronze to be produced in yttrium oxide, monoclinic tungsten oxide and hexagonal phase. Tungsten-tungsten bronze, it is not easy to obtain doped green pyrochlore and hexagonal composite yttrium-tungsten bronze; for example, when the M metal element is lanthanum (Cs), when the heating reduction reaction time expires (more than 12 hours) ), it is easy to make the antimony-doped tungsten bronze unstable in the pyrochlore and hexagonal composite crystal phase, and develop to the hexagonal crystal phase and generate a large amount of purple tungsten. It is worth noting that when the weight ratio of the tungsten-containing precursor to the hydroxamic acid chelating agent is between about 30 and 25, less than this ratio (for example, the weight ratio of the tungsten-containing precursor to the hydroxamic acid chelating agent) Less than 25) will form metal tungsten. Above this ratio, the coordination effect of stabilizing tungsten and metal ions on oxygen is not good, and the use of hydroxamic acid chelating agent will leave trace carbon element in powder after completion of tungsten bronze crystal. in.
為了讓本發明之上述和其他目的、特徵、和優點能更明顯易懂，下文特舉數實施例配合所附圖示，作詳細說明如下： The above and other objects, features, and advantages of the present invention will become more apparent and understood.
近紅外光阻隔材料的製備Preparation of near-infrared light blocking material
【比較例1】 [Comparative Example 1]
將30g偏鎢酸銨與1.0g水楊基羥肟酸與8.8g氯化銫加入100ml去離子水中混合均勻，將配置好的上述溶液倒入不銹鋼密閉反應釜中，在80℃下恆溫加熱反應11小時後，進行銫氧化鎢前驅物粉體去水乾燥，於50℃低溫烘箱中乾燥24小時。再將銫氧化鎢前驅物粉體放置於高溫反應爐中進行粉體燒結，高溫爐持續加熱至750℃反應8小時，得到粉體產物，平均一次粒徑約29nm。 30 g of ammonium metatungstate and 1.0 g of salicyl hydroxamic acid and 8.8 g of cerium chloride were added to 100 ml of deionized water and mixed uniformly. The prepared solution was poured into a stainless steel closed reaction kettle, and the reaction was heated at 80 ° C under constant temperature. After 11 hours, the tungsten oxide precursor powder was dehydrated and dried in a low temperature oven at 50 ° C for 24 hours. The tantalum tungsten oxide precursor powder is placed in a high temperature reaction furnace for powder sintering, and the high temperature furnace is continuously heated to 750 ° C for 8 hours to obtain a powder product having an average primary particle diameter of about 29 nm.
以X光繞射儀(X-Ray Diffractometer，XRD)分析產物，得知該產物是由焦綠石(pyrochlore)與六方晶相鎢青銅(hexagonal tungsten bronzes、HTB)所複合組成。以X-ray光電子能譜(X-ray photoelectron spectrometer、XPS)對所得之產物進行分析，得知Cs與W的比例為0.38：1(預測所得產物符合化學式Cs0.38WO3)。以紅外線碳分析儀定量分析上述產物中的碳殘留量，得知焦綠石(pyrochlore)與六方晶相鎢青銅(hexagonal tungsten bronzes、HTB)所複合組成銫鎢青銅產物的碳殘留量為5ppm。接著，量測該產物對波長300nm至2500nm的光穿透圖譜，結果請參照第2圖；以及， 將該樣品進行紫外光加速老化測試(QUV)，使用紫外光波長313nm的光源以能量3.1W/m2進行500小時測試，量測該測試產物對波長300nm至2500nm的光穿透圖譜，結果請參照第2圖。對該光穿透圖譜之波長950nm與1450nm的穿透率數值進行變化差異分析，結果如表1所示。 The product was analyzed by X-ray Diffractometer (XRD) and found to be composed of pyrochlore and hexagonal tungsten bronzes (HTB). The obtained product was analyzed by X-ray photoelectron spectrometer (XPS) to find that the ratio of Cs to W was 0.38:1 (the predicted product was in accordance with the chemical formula Cs 0.38 WO 3 ). The amount of carbon residue in the above product was quantitatively analyzed by an infrared carbon analyzer, and it was found that the carbon residue of the composition of the yttrium-tungsten bronze product composed of pyrochlore and hexagonal tungsten bronzes (HTB) was 5 ppm. Next, the light penetration spectrum of the product for a wavelength of 300 nm to 2500 nm is measured. For the result, refer to FIG. 2; and, the sample is subjected to an ultraviolet accelerated aging test (QUV) using a light source having an ultraviolet wavelength of 313 nm at an energy of 3.1 W. /m 2 was subjected to a 500-hour test, and the light penetration pattern of the test product for a wavelength of 300 nm to 2500 nm was measured. For the result, refer to FIG. The difference in the transmittance values of the wavelengths of 950 nm and 1450 nm of the light transmission pattern was analyzed, and the results are shown in Table 1.
【實施例1】 [Example 1]
將30g偏鎢酸銨與1.0g水楊基羥肟酸與8.8g氯化銫及3.0g碳酸加入98ml去離子水中混合均勻，將配置好的上述溶液倒入不銹鋼密閉反應釜中，在80℃下恆溫加熱反應11小時後，進行銫氧化鎢前驅物粉體去水乾燥，於50℃低溫烘箱中乾燥24小時。再將銫氧化鎢前驅物粉體放置於高溫反應爐中進行粉體燒結，高溫爐持續加熱至750℃反應8小時，得到粉體產物，平均一次粒徑約24nm。 30 g of ammonium metatungstate and 1.0 g of salicyl hydroxamic acid and 8.8 g of cerium chloride and 3.0 g of carbonic acid were added to 98 ml of deionized water and uniformly mixed. The prepared solution was poured into a stainless steel closed reaction kettle at 80 ° C. After heating at a constant temperature for 11 hours, the tungsten oxide precursor powder was dehydrated and dried in a low temperature oven at 50 ° C for 24 hours. Then, the tungsten oxide tungsten precursor powder is placed in a high temperature reaction furnace for powder sintering, and the high temperature furnace is continuously heated to 750 ° C for 8 hours to obtain a powder product having an average primary particle diameter of about 24 nm.
以X光繞射儀(X-Ray Diffractometer，XRD)分析產物，得知該產物是由焦綠石(pyrochlore)與六方晶相鎢青銅(hexagonal tungsten bronzes、HTB)所複合組成。以X-ray光電子能譜(X-ray photoelectron spectrometer、XPS)對所得之產物進行分析，得知Cs與W的比例為0.36：1(預測所得產物符合化學式Cs0.36WO3)。以紅外線碳分析儀定量分析上述產物中的碳殘留量，得知焦綠石(pyrochlore)與六方晶相鎢青銅(hexagonal tungsten bronzes、HTB)所複合組成銫鎢青銅產物的碳殘留量為15ppm。接著，量測該產物對波 長300nm至2500nm的光穿透圖譜；以及，將該樣品進行紫外光加速老化測試(QUV)，使用紫外光波長313nm的光源以能量3.1W/m2進行500小時測試，量測該測試產物對波長300nm至2500nm的光穿透圖譜。對該光穿透圖譜之波長950nm與1450nm的穿透率數值進行變化差異分析，結果如表1所示。 The product was analyzed by X-ray Diffractometer (XRD) and found to be composed of pyrochlore and hexagonal tungsten bronzes (HTB). The obtained product was analyzed by X-ray photoelectron spectrometer (XPS) to find that the ratio of Cs to W was 0.36:1 (the predicted product was in accordance with the chemical formula Cs 0.36 WO 3 ). The amount of carbon residue in the above product was quantitatively analyzed by an infrared carbon analyzer, and it was found that the carbon residue of the composition of the yttrium-tungsten bronze product of pyrochlore and hexagonal tungsten bronzes (HTB) was 15 ppm. Next, the light transmission spectrum of the product to a wavelength of 300 nm to 2500 nm is measured; and the sample is subjected to an ultraviolet accelerated aging test (QUV), and the light source of the ultraviolet light having a wavelength of 313 nm is tested at an energy of 3.1 W/m 2 for 500 hours. The light transmission pattern of the test product to a wavelength of 300 nm to 2500 nm was measured. The difference in the transmittance values of the wavelengths of 950 nm and 1450 nm of the light transmission pattern was analyzed, and the results are shown in Table 1.
【實施例2】 [Example 2]
將30g偏鎢酸銨與1.0g水楊基羥肟酸與6.8g碳酸銫加入98ml去離子水中混合均勻，將配置好的上述溶液倒入不銹鋼密閉反應釜中，在80℃下恆溫加熱反應11小時後，進行銫氧化鎢前驅物粉體去水乾燥，於50℃低溫烘箱中乾燥24小時。再將銫氧化鎢前驅物粉體放置於高溫反應爐中進行粉體燒結，高溫爐持續加熱至750℃反應8小時，得到粉體產物，平均一次粒徑約28nm。 30 g of ammonium metatungstate and 1.0 g of salicyl hydroxamic acid and 6.8 g of cesium carbonate were added to 98 ml of deionized water and mixed uniformly. The prepared solution was poured into a stainless steel closed reaction kettle, and the reaction was heated at 80 ° C under constant temperature. After an hour, the tungsten oxide precursor powder was dehydrated and dried in a low temperature oven at 50 ° C for 24 hours. Then, the tungsten oxide tungsten precursor powder is placed in a high temperature reaction furnace for powder sintering, and the high temperature furnace is continuously heated to 750 ° C for 8 hours to obtain a powder product having an average primary particle diameter of about 28 nm.
以X光繞射儀(X-Ray Diffractometer，XRD)分析產物，得知該產物是由焦綠石(pyrochlore)與六方晶相鎢青銅(hexagonal tungsten bronzes、HTB)所複合組成。以X-ray光電子能譜(X-ray photoelectron spectrometer、XPS)對所得之產物進行分析，得知Cs與W的比例為0.35：1(預測所得產物符合化學式Cs0.35WO3)。以紅外線碳分析儀定量分析上述產物中的碳殘留量，得知焦綠石(pyrochlore)與六方晶相鎢青銅(hexagonal tungsten bronzes、HTB)所複合組成銫 鎢青銅產物的碳殘留量為30ppm。接著，量測該產物對波長300nm至2500nm的光穿透圖譜；以及，將該樣品進行紫外光加速老化測試(QUV)，使用紫外光波長313nm的光源以能量3.1W/m2進行500小時測試，量測該測試產物對波長300nm至2500nm的光穿透圖譜。對該光穿透圖譜之波長950nm與1450nm的穿透率數值進行變化差異分析，結果如表1所示。 The product was analyzed by X-ray Diffractometer (XRD) and found to be composed of pyrochlore and hexagonal tungsten bronzes (HTB). The obtained product was analyzed by X-ray photoelectron spectrometer (XPS) to find that the ratio of Cs to W was 0.35:1 (the predicted product was in accordance with the chemical formula Cs 0.35 WO 3 ). The carbon residue in the above product was quantitatively analyzed by an infrared carbon analyzer, and it was found that the carbon residue of the composition of the yttrium-tungsten bronze product composed of pyrochlore and hexagonal tungsten bronzes (HTB) was 30 ppm. Next, the light transmission spectrum of the product to a wavelength of 300 nm to 2500 nm is measured; and the sample is subjected to an ultraviolet accelerated aging test (QUV), and the light source of the ultraviolet light having a wavelength of 313 nm is tested at an energy of 3.1 W/m 2 for 500 hours. The light transmission pattern of the test product to a wavelength of 300 nm to 2500 nm was measured. The difference in the transmittance values of the wavelengths of 950 nm and 1450 nm of the light transmission pattern was analyzed, and the results are shown in Table 1.
【實施例3】 [Example 3]
將30g偏鎢酸銨與1.0g水楊基羥肟酸與6.8g碳酸銫及2.0g碳酸加入98ml去離子水中混合均勻，將配置好的上述溶液倒入不銹鋼密閉反應釜中，在80℃下恆溫加熱反應11小時後，進行銫氧化鎢前驅物粉體去水乾燥，於50℃低溫烘箱中乾燥24小時。再將銫氧化鎢前驅物粉體放置於高溫反應爐中進行粉體燒結，高溫爐持續加熱至750℃反應8小時，得到粉體產物，平均一次粒徑約25nm。 Mix 30g of ammonium metatungstate with 1.0g of salicyl hydroxamic acid and 6.8g of cesium carbonate and 2.0g of carbonic acid into 98ml of deionized water, and pour the prepared solution into a stainless steel closed reactor at 80 °C. After heating at a constant temperature for 11 hours, the tungsten oxide precursor powder was dehydrated and dried in a low temperature oven at 50 ° C for 24 hours. Then, the tungsten oxide tungsten precursor powder is placed in a high temperature reaction furnace for powder sintering, and the high temperature furnace is continuously heated to 750 ° C for 8 hours to obtain a powder product having an average primary particle diameter of about 25 nm.
以X光繞射儀(X-Ray Diffractometer，XRD)分析產物，請參照第3圖。由第3圖可知，該產物是由焦綠石(pyrochlore)與六方晶相鎢青銅(hexagonal tungsten bronzes、HTB)所複合組成。以X-ray光電子能譜(X-ray photoelectron spectrometer、XPS)對所得之產物進行分析，得知Cs與W的比例為0.35：1(預測所得產物符合化學式Cs0.35WO3)。以紅外線碳分析儀定量分析上述產物中的碳酸 觸媒殘留量，得知焦綠石(pyrochlore)與六方晶相鎢青銅(hexagonal tungsten bronzes、HTB)所複合組成銫鎢青銅產物的碳殘留量為45ppm。接著，量測該產物對波長300nm至2500nm的光穿透圖譜，結果請參照第4圖；以及，將該樣品進行紫外光加速老化測試(QUV)，使用紫外光波長313nm的光源以能量3.1W/m2進行500小時測試，量測該測試產物對波長300nm至2500nm的光穿透圖譜，結果請參照第4圖。對該光穿透圖譜之波長950nm與1450nm的穿透率數值進行變化差異分析，結果如表1所示。 The product was analyzed by X-ray Diffractometer (XRD), please refer to Figure 3. As can be seen from Fig. 3, the product is composed of pyrochlore and hexagonal tungsten bronzes (HTB). The obtained product was analyzed by X-ray photoelectron spectrometer (XPS) to find that the ratio of Cs to W was 0.35:1 (the predicted product was in accordance with the chemical formula Cs 0.35 WO 3 ). The residual amount of carbonic acid catalyst in the above product was quantitatively analyzed by an infrared carbon analyzer, and the carbon residue of the composition of the yttrium-tungsten bronze product of pyrochlore and hexagonal tungsten bronzes (HTB) was found to be 45ppm. Next, the light transmission spectrum of the product to a wavelength of 300 nm to 2500 nm is measured. For the result, refer to FIG. 4; and the sample is subjected to an ultraviolet accelerated aging test (QUV) using a light source having an ultraviolet wavelength of 313 nm at an energy of 3.1 W. /m 2 was subjected to a 500-hour test, and the light penetration pattern of the test product for a wavelength of 300 nm to 2500 nm was measured. For the result, please refer to FIG. The difference in the transmittance values of the wavelengths of 950 nm and 1450 nm of the light transmission pattern was analyzed, and the results are shown in Table 1.
【實施例4】 [Embodiment 4]
將30g偏鎢酸銨與1.0g水楊基羥肟酸與7.0g碳酸銫及4.8g碳酸加入95ml去離子水中混合均勻，將配置好的上述溶液倒入不銹鋼密閉反應釜中，在80℃下恆溫加熱反應11小時後，進行銫氧化鎢前驅物粉體去水乾燥，於50℃低溫烘箱中乾燥24小時。再將銫氧化鎢前驅物粉體放置於高溫反應爐中進行粉體燒結，高溫爐持續加熱至750℃反應8小時，得到粉體產物，平均一次粒徑約22nm。 Mix 30g ammonium metatungstate with 1.0g salicyl hydroxamic acid with 7.0g cesium carbonate and 4.8g carbonic acid in 95ml deionized water, and pour the prepared solution into stainless steel closed reactor at 80 °C After heating at a constant temperature for 11 hours, the tungsten oxide precursor powder was dehydrated and dried in a low temperature oven at 50 ° C for 24 hours. Then, the tungsten oxide tungsten precursor powder is placed in a high temperature reaction furnace for powder sintering, and the high temperature furnace is continuously heated to 750 ° C for 8 hours to obtain a powder product having an average primary particle diameter of about 22 nm.
以X光繞射儀(X-Ray Diffractometer，XRD)分析產物，得知該產物是由焦綠石(pyrochlore)與六方晶相鎢青銅(hexagonal tungsten bronzes、HTB)所複合組成。以X-ray光電子能譜(X-ray photoelectron spectrometer、XPS)對所得之產物進行分析，得知Cs與W的比例為0.39：1(預測所 得產物符合化學式Cs0.39WO3)。以紅外線碳分析儀定量分析上述產物中的碳殘留量，得知焦綠石(pyrochlore)與六方晶相鎢青銅(hexagonal tungsten bronzes、HTB)所複合組成銫鎢青銅產物的碳殘留量為77ppm。接著，量測該產物對波長300nm至2500nm的光穿透圖譜；以及，將該樣品進行紫外光加速老化測試(QUV)，使用紫外光波長313nm的光源以能量3.1W/m2進行500小時測試，量測該測試產物對波長300nm至2500nm的光穿透圖譜。對該光穿透圖譜之波長950nm與1450nm的穿透率數值進行變化差異分析，結果如表1所示。 The product was analyzed by X-ray Diffractometer (XRD) and found to be composed of pyrochlore and hexagonal tungsten bronzes (HTB). The obtained product was analyzed by X-ray photoelectron spectrometer (XPS) to find that the ratio of Cs to W was 0.39:1 (the predicted product conformed to the chemical formula Cs 0.39 WO 3 ). The carbon residue in the above product was quantitatively analyzed by an infrared carbon analyzer, and it was found that the carbon residue of the yttrium-tungsten bronze product composed of pyrochlore and hexagonal tungsten bronzes (HTB) was 77 ppm. Next, the light transmission spectrum of the product to a wavelength of 300 nm to 2500 nm is measured; and the sample is subjected to an ultraviolet accelerated aging test (QUV), and the light source of the ultraviolet light having a wavelength of 313 nm is tested at an energy of 3.1 W/m 2 for 500 hours. The light transmission pattern of the test product to a wavelength of 300 nm to 2500 nm was measured. The difference in the transmittance values of the wavelengths of 950 nm and 1450 nm of the light transmission pattern was analyzed, and the results are shown in Table 1.
由第2及4圖以及表1可知，本發明所述之近紅外光阻隔材料(實施例3)，在近紅外光的耐候測試中 (QUV-500小時)具有極為穩定的光譜表現，光譜差異率小於3%。在碳酸觸媒的使用之下，可以提升此近紅外光阻隔材料的穩定性達5%以上。此外，實施例2與實施例3相比，碳酸觸媒的重量百分比在整體反應物的6.3%時，具有最佳的抗QUV特性，可以近紅外光波長數值差異控制在3%以下。在過多的碳酸觸媒添加之下，會使銫鎢青銅的還原穩定性變差，導致近紅外光阻隔率變異變大。值得注意的是，碳酸觸媒對於整體化合物液體重量比值與羥肟酸螯合劑對鎢青銅粉體的碳元素殘留有明顯的影響，碳酸觸媒的比值越高粉體含碳量高。 It can be seen from FIGS. 2 and 4 and Table 1 that the near-infrared light blocking material (Example 3) of the present invention is used in the weathering test of near-infrared light. (QUV-500 hours) has an extremely stable spectral performance with a spectral difference of less than 3%. Under the use of carbonic acid catalyst, the stability of this near-infrared light blocking material can be improved by more than 5%. Further, in Example 2, compared with Example 3, the weight percentage of the carbonic acid catalyst has an optimum anti-QUV characteristic at 6.3% of the total reactant, and the difference in the wavelength value of the near-infrared light can be controlled to 3% or less. Under the addition of too much carbonic acid catalyst, the reduction stability of the tantalum tungsten bronze is deteriorated, resulting in a large variation in the near-infrared light blocking ratio. It is worth noting that the carbonic acid catalyst has a significant effect on the overall compound liquid weight ratio and the hydroxamic acid chelating agent on the carbon residue of the tungsten bronze powder. The higher the ratio of the carbonic acid catalyst, the higher the carbon content of the powder.
雖然本發明已以數個較佳實施例揭露如上，然其並非用以限定本發明，任何熟習此技藝者，在不脫離本發明之精神和範圍內，當可作任意之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。 While the invention has been described above in terms of several preferred embodiments, it is not intended to limit the invention, and the invention may be modified and modified without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims.
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