201249896 六、發明說明： 【發明所屬之技術領域】 材料有關’本創作係提供—種電磁波吸收 【先前技術】 少曰^前的微波吸收材料以鐵氧體居多，還有碳黑、金屬 電高分子等吸收體，單一吸收體吸波頻帶ί限， ，像鐵乳體此類吸收劑由於姉密度大對飛行器隱形 此可以採取複合的方法將對不同頻帶吸收有利的介質材 ίί=起，以達到寬頻吸收的目的。為了實現質輕的要求，ΐ 用貝輕的有機聚合物作基體，無機吸收材料作為客體， 合型微波吸收材料就成了必然趨勢。而且具有共軛電子結 利用摻雜而成的導電聚合物(聚苯胺)，本身就有較好的微波吸 收性能。吸波材料中所用的吸波劑大多是鐵氧體、導電金屬、 鐵電^料、導電高分手等材料，利用它們與黏合劑以不同的比 例及複合方式等途徑來調整吸波材料的參數，達到吸波的目 的。例如’雙層結構磁介質材料(double妨erstructuremagnetic mediums)、鐵電 /鐵磁複合材料(ferr〇electric/fem)magnetic compp^tes)、導電金屬/鐵氧磁體複合材料(Ag/fenite)、鐵磁/ 石墨複合材料(FesOVgraphite)、鐵磁/導電高分子複合材料 (ferrite/polymer)等。 ,中華民國專利469283中申明之介電性電磁波吸收材料之 $造方法因混合後之藥漿(Slurry)黏度大，首先以樹脂混合部份 石厌黑以特殊設計的3000-6000rpm高速研磨機分散，再添加碳 粉、f電纖維及中空球’此時藥漿黏度大增，改用3〇〇_6〇〇rpm ，速咼黏度攪拌機充分混合後^_塗佈成試片，製程及設備較繁 複’且所使用的導電填料皆為化學合成物，極不符合目前全球 科技產業對環保之需求。中華民國專利567643中申明之改良 型Salbmy Screen式電磁波吸收材以兩種材料複合而成，其中 201249896 第-層為電性均質耗損材，第二層為低介電常紐，這類雔声 t料ff作上比單層材料之製程較繁複。美國專利646509^2 Γίί相生成法所1^的碳纖維取代傳統的碳纖維，雖缺碳望 ，纖維，加量，低’但所使⑽導電填料皆為化學合成 物’亚不符合目前高科技產業對環保之需求華 5_7中申明以多層中空碳球含量5_5_%混合 磁波吸收材’所使用的彡層巾空碳球亦為化學合成物 合目前全球科技產業對環保之需求。 个付 【發明内容】 雲於上述習知技狀缺點，本辦之主要目的係提供 J磁J吸收材餘錢及錄備綠，她独往技術:、 ^程間早、成本低廉與符合現今環保需求之優點，並可依昭 ㈣收的需要調整添加物比例，達酬需微波吸收頻，圍，、 同時可作為微波吸收及紅外線遮蔽材料應用。 本創作係提供-種電磁波吸收材料^成物，係在苯胺 過程中加入鋇鐵氧(BaFe^O,9)、鈦酸鋇(BaTi〇3)為填料人: 具有磁性/介電性核及導電殼之核殼型複合㈣，得 ^ 波吸收材料組成物。 彳电磁 本創作係提供一種電磁波吸收材料組成物之製備方法，立 步驟為：（1)製作鋇鐵氧與鈦酸鋇混合之水溶液 二 院基苯續酸(DBS顺苯胺(編lne)混合之乳化液；: 水溶液加入(2)之乳化液，再加入過硫酸銨(Aps)，使其產 合反應；（4)聚合反應結束後加人_，使⑶之混合^ : 下兩層，取下層沉澱物過驗，進行供乾處理，所製得之 ^te+BaTl〇3)/PANI複合物即為一電磁波吸收材料組^ 〇〇 ° 以上之概述與接下來的詳細說明及附圖，皆 步說明本創作達到預定目的聰取的方式、手 關本創作的其他目的及優點，將在後續的說明及圖示中加 201249896 【實施方式】 …^下#藉&特定的具體實例說明本創作之實施方式，熟悉 #明書所揭示之内雜祕瞭解本創作 ( 跡-^本_之電磁波吸收材料組成物之製備方法步 二Z所不’其步驟為：⑴製作鋇鐵氧與鈦酸鋇混 G1 ; (2)製料二烧基料_bsa)與苯胺 混合之乳化液S02; (3)將⑴之水溶液加之乳化 1庫硫酸銨_)，使其產生聚合反應S03; (4)聚合 1ΐΓ:Ή〇3 陶^ jl：)^肖酸鋇、顧鐵、甘胺酸為原料以莫耳比1: η 5: f的比例加入適當去離子水混合祕ls分鐘 1 =水調節溶液pH值為7。並在财c油浴下加埶得到 放進烘箱24小時成凝膠。凝膠在加執 燃^成疏鬆灰色粉體嘴上述粉體在高溫爐 敌ψ媒口 # 〇C、7 〇C、85〇C各溫度下锻燒3小時冷卻後 取出^ j研磨’便得到所需鋇鐵氧磁體(Β^2〇19)粉末。s!i 在jiii1!01欽酸四正丁醋溶於異丙醇中，攪拌30分鐘。 ^丨 加人aimd乙酸鋇使其溶解。用冰醋酸調 真空乾：===應置於 =:9GG°C下雜，冷卻後取出研磨得到__^ (3)將鎖鐵氧磁體與欽酸頻各5克加入去離子水 ^於201249896 VI. Description of the invention: [Technical field to which the invention belongs] Materials related to 'This creation provides a kind of electromagnetic wave absorption 【Prior Art】 The microwave absorption materials before the 曰 曰 ^ are mostly ferrite, as well as carbon black and metal Molecular absorbers, single absorbers, absorbing bands, such as iron emulsions, such as iron emulsions, due to the high density of the sputum, the aircraft can be invisible, which can adopt a composite method to absorb favorable dielectric materials for different frequency bands. Achieve broadband absorption. In order to achieve the requirements of light weight, 贝 using light organic polymer as the matrix and inorganic absorbing material as the guest, the combined microwave absorbing material has become an inevitable trend. Moreover, the conductive polymer (polyaniline) which is doped with a conjugated electron junction has a good microwave absorption property. Most of the absorbing agents used in absorbing materials are ferrite, conductive metals, ferroelectric materials, conductive high-strength materials, etc., and they are used to adjust the parameters of absorbing materials by different ratios and composite methods. To achieve the purpose of absorbing waves. For example, 'double erstructure magnetic mediums, ferr〇electric/fem magnetic compp^tes, conductive metal/ferromagnetic composites (Ag/fenite), iron Magnetic/graphite composite (FesOVgraphite), ferromagnetic/conductive polymer composite (ferrite/polymer). The method for fabricating the dielectric electromagnetic wave absorbing material declared in the Republic of China Patent No. 469283 is because the viscosity of the mixed slurry (Slurry) is large, and firstly, the resin is partially mixed with a black stone and dispersed by a specially designed 3000-6000 rpm high-speed grinder. , then add carbon powder, f electric fiber and hollow ball' At this time, the viscosity of the slurry is greatly increased, and it is changed to 3〇〇_6〇〇 rpm, and the quick-drying viscosity mixer is fully mixed, and then coated into test pieces, process and equipment. The more complicated 'and the conductive fillers used are chemical compounds, which is inconsistent with the current environmental protection needs of the global technology industry. The modified Salbmy Screen electromagnetic wave absorbing material declared in the Republic of China Patent No. 567643 is compounded by two materials, wherein 201249896 the first layer is an electrical homogeneous consumable material, and the second layer is a low dielectric constant nucleus. The material ff is more complicated than the single layer material. The carbon fiber of the US patent 646509^2 Γίί phase generation method replaces the traditional carbon fiber, although the carbon deficiency, fiber, addition, low 'but the (10) conductive filler is a chemical composition 'Asia does not meet the current high-tech industry The demand for environmental protection Hua 5_7 declares that the multi-layer hollow carbon sphere content of 5_5_% mixed magnetic wave absorbing material used in the 彡 layer of hollow carbon ball is also a chemical synthesis of the current global technology industry demand for environmental protection.付付[Summary] Cloud in the above-mentioned shortcomings of the prior art, the main purpose of the Office is to provide J magnetic J absorbent material and record green, her unique technology:, early, low cost and in line with the present The advantages of environmental protection needs, and the proportion of additives can be adjusted according to the needs of Zhao (4), and the microwave absorption frequency, circumference, and microwave absorption and infrared shielding materials can be applied. This creation provides a kind of electromagnetic wave absorbing material, which is added with barium ferrite (BaFe^O, 9) and barium titanate (BaTi〇3) as fillers in the process of aniline: magnetic/dielectric core and The core-shell composite of the conductive shell (4) obtains a wave absorbing material composition.彳 本 本 本 本 本 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳 彳Emulsion;: Add the emulsion of (2) to the aqueous solution, add ammonium persulfate (Aps) to make the reaction; (4) Add the mixture after the end of the polymerization, and mix the mixture with (3): The lower layer of the precipitate is subjected to dry treatment, and the obtained ^te+BaTl〇3)/PANI composite is an electromagnetic wave absorbing material group. 〇〇° The above summary and the following detailed description and drawings, Step by step to explain the way in which the creation achieves the intended purpose, and the other purposes and advantages of the creation of the handwriting, will be added to the subsequent description and illustration 201249896 [Embodiment] ...^下#借&specific examples The implementation method of this creation is familiar with the secrets revealed by #明书 to understand the creation (the method of preparing the electromagnetic wave absorbing material composition of the trace-^本_step 2 Z is not] the steps are as follows: (1) making ferrocene and Barium titanate mixed with G1; (2) Two-base base material _bsa) and benzene An amine mixed emulsion S02; (3) The aqueous solution of (1) is added with emulsified 1 library ammonium sulfate _) to produce a polymerization reaction S03; (4) Polymerization 1 ΐΓ: Ή〇 3 陶 ^ jl:) ^ 钡 钡 钡, Gu Iron and glycine are used as raw materials in a ratio of molar ratio 1: η 5: f to the appropriate deionized water to mix the secret ls minutes 1 = the pH of the water-conditioning solution is 7. The crucible was added under the c-oil bath and placed in an oven for 24 hours to form a gel. The gel is added to the smoldering powder into the loose gray powder mouth. The above powder is calcined in the high temperature furnace enemy medium # 〇C, 7 〇C, 85 〇C for 3 hours and then cooled and then taken out. The required barium ferrite magnet (Β^2〇19) powder. s!i Dissolve in isopropyl alcohol in jiii1!01 tetradecanoic vinegar and stir for 30 minutes. ^丨 Add aimd acetate to dissolve it. Adjust with glacial acetic acid and vacuum: === should be placed at =9GG °C, and after cooling, remove and grind to get __^ (3) Add 5 grams of lock ferrite magnet and acid acid to deionized water.
S 5 201249896 燒杯中’在室溫下超音波震盪攪拌1小時。將〇.lmol十二烷 基苯續酸(DBSA)加入裝有300 ml去離子水中的四口燒瓶，機 械攪拌10 min後加入1〇克苯胺(Aniline)乳化30 min。將上述 超音波震盪攪拌後之鋇鐵氧磁體與鈦酸鋇混合之水溶液加入 預先擾拌混合之DBSA-Aniline乳化液中在超音波授拌1小 時。S13 (4) 取〇，1 mol過硫酸銨(APS)加入200 ml的去離子水，授 拌1個小時後’在30分鐘内逐滴加入上述⑶乳化液中。在〇〜5 C條件下持續反應12小時，聚合反應結束加入丙酮使其分為· 上下兩層，取下層沈澱物利用減壓過濾完成後，置於6〇。〇之 烘箱’烘乾時間24小時，製得(BaFerrite+BaTi03)/PANHI合 物。S14 (5) 將液態樹脂與（Ba Ferrite+BaTi03)/PANI複合物以 65:35之重量比混合，以機械攪拌混料後灌入模具，經熟化冷 卻後，自模具中即可獲取厚度為〇 5mm-5.0mm，在18-40GHz 頻率範圍内具10dB以上反射損失之具紅外線遮蔽及微波吸收 功能之材料成品。S15 。圖3係為具體實施例之成品與其他材料相比較之微波反 射損失特性示意圖，其中reflecti〇n l〇ss代表反射損失、單位 為dB ^ Frequency代表吸收頻率、單位為GHz ;⑷為複合物 之低頻微波(2-18GHZ)反射損失分析；在低頻微波吸收測試結 果三BaFei2〇i9的最大吸收頻率約在11 Giiz，dB = -4 ; BaTi03 的最大吸收頻率約在 6.8 GHz，dB = _9 ; (Ba ferrite+BaTic>3) 複合物最大吸收頻率約在9.8 GHz，dB = -7.5 ; (Ba femte+BaTi〇3)/PANI複合物最大吸收頻率約在7 5 GHz，犯= jO。測試結果(Ba ferrite+BaTiC^/PANI複合物有較佳的反射 損失。（b)為複合物之高頻微波(184〇GHz)反射損失分析； BaFei2〇19 的最大吸收頻率約在 32.5 GHz，dB = -12 ; BaTi03 具有雙吸收峰，吸收頻率約在19 5 GHz，dB = ·22與％ 5 GHz ’ dB = -19，在 dB = -10 時的頻寬為 15 GHz (19_2〇 5 GHz) 201249896 與 2 GHz (31.5-33.5 GHz)。（Ba ferrite+BaTi03)複合物具有雙 吸收峰，吸收頻率約在31 GHz，dB = -12與38.2 GHz^ dB^ -33 ’ 在 dB = ·10 時的頻寬為15(}112(3〇 2_317〇}明與4(^2 (36-40 GHz) ; (Ba ferrite+BaTi03)/PANI 複合物亦具有雙吸收 峰，吸收頻率約在 22 GHz，dB = -18 與 36 GHz，dB = -22， 在 dB = -10 時的頻寬為 2.5 GHz (21.3-23.2 GHz)與 4 GHz (34-38 GHz)。測試結果（Ba ferrite+BaTi〇3)/PANI 複合物在 18-40GHz頻帶範圍有較佳的吸收效果。 圖4係為具體實施例之成品與其他材料相比較之埶成像 分析圖’如圖所示’⑻為中紅外波段(3_5磁)熱影像圖，從圖 中可發現純PE的最大溫度及平均溫度為7⑻及496。〇，當加 入微量的PANI (0.02 g/cm3)最大溫度及平均溫度降為669及 W2 °C ;加入BaTi〇3後最大溫度及平均溫度降為622及358 °C ;加入BaFe^Ow後最大溫度及平均溫度降為613及346 °C ;加^(Ba ferrite+BaTiO3)後最大溫度及平均溫度降為465 及237 T：;加入(Ba ferrite+BaTiC^/PAM複合物後最大溫度 及平均溫度降為453及226 〇C。，PE膠>}的表面溫度隨著樣 。口的加入明顯地下降’其中以（Ba ferrite+BaTi〇3)/pANI複合 物效果最佳，平均溫度約減少26G t。圖遠紅外波段 (8-12 um)熱影像圖，如圖所示可發現其結果與中红外波段相 同，隨著樣品的加入溫度隨之明顯下降，顯示 f^rri請aTi〇3)/PANI複合她纽降低紅外雜 達到遮蔽效果。 h上述之實關僅為例示性·本創作之特點及其功效，而 非用於限縣創作之實質技術内容的侧。任何熟習此技藝之 ϋ"?可在树背賴作之精神及範訂，對上述實施例進行 變化。因此，本創作之削保護軸 專利範圍所列。 201249896 【圖式簡單說明】 圖1係為本創作之電磁波吸收材料組成物之製備方法步 驟不意圖。 圖2係為本創作之具體實施例之具紅外線遮蔽及微波吸 收功能之材料製備方法步驟示意圖。 圖3係為具體實施例之成品與其他材料相比較之微波反 射損失特性示意圖。 圖4係為具體實施例之成品與其他材料相比較之熱成像 分析圖。 【主要元件符號說明】 S01〜S04 :流程步驟 S11〜S15 :流程步驟S 5 201249896 In a beaker, stir at room temperature for 1 hour with ultrasonic vibration. 〇.lmol of dodecylbenzene benzoic acid (DBSA) was added to a four-necked flask containing 300 ml of deionized water, mechanically stirred for 10 min, and then emulsified by adding an gram of aniline for 30 min. The aqueous solution of the above-mentioned ultrasonically oscillated and stirred barium ferrite magnet and barium titanate was added to the pre-scrambled mixed DBSA-Aniline emulsion for ultrasonic mixing for 1 hour. S13 (4) Take hydrazine, add 1 mol of ammonium persulfate (APS) to 200 ml of deionized water, and mix for 1 hour, then add dropwise to the above (3) emulsion within 30 minutes. The reaction was continued for 12 hours under the conditions of 〇~5 C, and acetone was added to the upper end of the polymerization reaction to separate the upper and lower layers, and the lower layer sediment was removed by filtration under reduced pressure, and then placed at 6 Torr. The oven was dried for 24 hours to obtain a (BaFerrite+BaTi03)/PANHI compound. S14 (5) The liquid resin and (Ba Ferrite+BaTi03)/PANI composite are mixed at a weight ratio of 65:35, mechanically stirred and mixed into the mold, and after being matured and cooled, the thickness can be obtained from the mold. 〇5mm-5.0mm, finished with infrared shielding and microwave absorption function with reflection loss of more than 10dB in the frequency range of 18-40GHz. S15. Figure 3 is a schematic diagram showing the microwave reflection loss characteristics of the finished product compared with other materials, wherein reflecti〇nl〇ss represents reflection loss, the unit is dB ^ Frequency represents the absorption frequency, and the unit is GHz; (4) is the low frequency of the composite. Microwave (2-18GHZ) reflection loss analysis; in the low-frequency microwave absorption test results, the maximum absorption frequency of BaFei2〇i9 is about 11 Giiz, dB = -4; the maximum absorption frequency of BaTi03 is about 6.8 GHz, dB = _9; Ferrite+BaTic>3) The maximum absorption frequency of the composite is about 9.8 GHz, dB = -7.5; (Ba femte+BaTi〇3)/PANI composite maximum absorption frequency is about 7 5 GHz, commit = jO. The test results (Ba ferrite+BaTiC^/PANI composite has better reflection loss. (b) is the high-frequency microwave (184 〇 GHz) reflection loss analysis of the composite; BaFei2〇19 has a maximum absorption frequency of about 32.5 GHz. dB = -12 ; BaTi03 has a double absorption peak with an absorption frequency of approximately 19 5 GHz, dB = ·22 and % 5 GHz ' dB = -19, and a bandwidth of 15 GHz at dB = -10 (19_2〇5 GHz) 201249896 and 2 GHz (31.5-33.5 GHz). (Ba ferrite+BaTi03) composite with double absorption peak, absorption frequency is about 31 GHz, dB = -12 and 38.2 GHz^ dB^ -33 ' at dB = ·10 The bandwidth is 15 (}112 (3〇2_317〇} and 4(^2 (36-40 GHz); (Ba ferrite+BaTi03)/PANI complex also has a double absorption peak, and the absorption frequency is about 22 GHz. , dB = -18 and 36 GHz, dB = -22, bandwidth is 2.5 GHz (21.3-23.2 GHz) and 4 GHz (34-38 GHz) at dB = -10. Test results (Ba ferrite+BaTi〇 3) / PANI composite has better absorption effect in the 18-40 GHz band. Figure 4 is the 埶 imaging analysis of the finished product compared with other materials as shown in the figure '(8) is the mid-infrared band ( 3_5 magnetic) heat Image, the maximum temperature and average temperature of pure PE can be found in the figure is 7 (8) and 496. 〇, when adding a small amount of PANI (0.02 g / cm3) maximum temperature and average temperature drop to 669 and W2 °C; adding BaTi〇 The maximum temperature and average temperature drop after 3 were 622 and 358 °C; the maximum temperature and average temperature drop after adding BaFe^Ow were 613 and 346 °C; the maximum temperature and average temperature drop after adding (Ba ferrite+BaTiO3) was 465. And 237 T:; after adding (Ba ferrite+BaTiC^/PAM composite, the maximum temperature and average temperature drop are 453 and 226 〇C. The surface temperature of PE glue >} is the same. The addition of the mouth is obviously decreased' Among them, the (Ba ferrite+BaTi〇3)/pANI composite has the best effect, and the average temperature is reduced by about 26G t. The far infrared band (8-12 um) thermal image map can be found as shown in the figure and the mid-infrared The band is the same, and the temperature of the sample is significantly decreased with the addition of the sample, indicating that f^rri please aTi〇3)/PANI compound her to reduce the infrared noise to achieve the shielding effect. h The above-mentioned actual customs are only the characteristics of the exemplary and original creations and their effects, and are not used for the side of the substantive technical content of the county creation. Any of the above-mentioned embodiments can be changed in the spirit and scope of the tree. Therefore, the creation of the cutting protection shaft is listed in the patent scope. 201249896 [Simple description of the drawing] Fig. 1 is a schematic diagram of the preparation method of the electromagnetic wave absorbing material composition of the present invention. Fig. 2 is a schematic view showing the steps of a method for preparing a material having infrared shielding and microwave absorbing functions according to a specific embodiment of the present invention. Fig. 3 is a schematic diagram showing the microwave reflection loss characteristics of the finished product of the specific embodiment compared with other materials. Figure 4 is a thermographic analysis of the finished embodiment of the embodiment compared to other materials. [Description of main component symbols] S01~S04: Process steps S11~S15: Process steps