(Journal of the Society of Materials Science, Japan), Vol. 62, No. 4, pp. 254-260, Apr. 2013 Fabrication of Superparamagnetic Wood Plastics Via In Situ Synthesis of Iron Oxide Nanoparticles in Wood Flour Derivatives by Yoshikuni TERAMOTO, Yusuke MATSUMOTO and Yoshiyuki NISHIO Wood flour (WF) was converted not only to carrier matrix for in situ synthesis of iron oxide nanoparticles but also to thermoplastic material by combination of anionic functionalization and benzylation. A sequence of procedure for the in situ synthesis of iron oxides includes ferrous ion-absorption of the chemically modified WF, precipitation of ferrous hydroxide by an alkaline treatment, and oxidation of the ferrous hydroxide. To facilitate the ferrous ion-absorption, we performed the anionic functionalization of WF via carboxymethylation or maleylation. The benzylation was expected to be favorable for improving thermoplasticity of the products. FT-IR spectroscopy revealed that the original hydroxyl groups were considerably substituted by the etherification and/or esterification. A successful incorporation of iron oxide particles (synthetic ferrites) into the anionically funcionalized WF matrix was confirmed by redox titrimetry. However, maleyl moieties incorporated after benzylation were largely hydrolyzed by the alkaline treatment for the in situ synthesis of iron oxides, which gave rise to an elution of ferric contents simultaneous with its formation. Such an elution could be prevented in part by the introduction of maleyl groups preceding benzylation. By means of the adequate set of chemical modifications, the original WF was transformed into a thermoplastic material. Actually, it was possible to mold the modified WF samples into a film form at a relatively low temperature of 140, even after the in situ synthesis of iron oxide. Magnetometry measurements revealed that the magnetic woody composite showed superparamagnetism (SPM) at room temperature. The unique magnetic character can be generally observed when the magnetic particles as dispersoid are loaded into the matrix on a scale of less than a few tens of nanometers. The formation of iron oxide nanoparticles was supported by field emission scanning electron microscopy and X-ray diffractometry. The observation of SPM may be of significance in the perceptibility to an external magnetic stimulus only on demand and without energy loss. Key words : Wood flour, Benzylation, Maleylation, Carboxymethylation, Magnetic nanocomposite, Thermoplastic, Superparamagnetism 1 1) 8) (DDS) in situ 1), 3) in situ (1) (2) NaOH Fe(OH) 2 (3) (IPN) 5) WF WF 24 8 6 Received Aug. 6, 2012 2013 The Society of Materials Science, Japan 606-8502 Graduate School of Agr., Kyoto Univ., Sakyo-ku, Kyoto, 606-8502 606-8502 Graduate School of Agr., Kyoto Univ., Sakyo-ku, Kyoto, 606-8502
255 (Fe-(CM-(HP-WF))) 7) 7) 9) 12) 13) WF 2 2 1 (a) WF J. Rettenmaier & Söhne GmbH + Co. KG LIGNOCEL S150TR 70 150μm 1 2 8h 40 1 (b) WF2.0g 200mL 20% 30mL 23 1h 14.7mL 100 3h 1 1 40 WF (Bz-WF) WF (Fe-(MA-WF)) (Bz-(Fe-(MA-WF)) (c) 500mL WF Bz-WF 1.5g 100mL 1.5mL 50g 23 16h 6h 40 WF Bz-WF MA-WF MA-(Bz- WF) (d) Bz-WF 1.5g 37.6mL 200mL 23 10min 30% 5mL 30min 60min 1.8mL 1.8g 30min 55 3.5h 200mL 70% 90% 70% 40 Bz-WF (CM-(Bz-WF)) (e) in situ 200mL WF WF 0.2g 100mL 0.025mol/L FeCl 2 23 24h 100mL 1mol/L NaOH 24 h 65 10mL 2wt% 30% 15min 1h 40 WF in situ Fe in situ Fe-(CM-(Bz-WF)) (f) 0.1mm 2min 5MPa 30s 10s 15MPa 30s (23 ) 15MPa 2min 2 2 (a) (II) (SnCl 2) Fe 2+ (K 2Cr 2O 7) % (b) FTIR-8600 KBr
256 Quantum Design Inc. (Superconducuting Quantum Interference Device : SQUID) MPMS-5 (H) (M) 100 298K 0G 50000G (= 5T) 1000G 0G Fig. 1 (FM) (SPM) M vs H (M s) SPM nm M s (1) L(x) = coth(x) 1/x Langevin μ k B T (Field Cooling, FC) (Zero Field Cooling, ZFC) (M vs T) FC 0.010T (= 100G) ZFC 300K 5K 0.010T (= 100G) 5K 300K ZFC FM SPM T B T B ZFC T max T B T max 14), 15) T B = βt max (β = 1.5 2) (FE-SEM) S-4800 Pt 1.6kV X (WAXD) Ultima- IV Ni CuKα (λ = 0.1542nm) 40kV 30mA 3 3 1 WF WF Bz-WF 36% in situ FT-IR Fig. 2b-2d 700 740cm 1 3200 3600cm 1 MA- (Bz-WF) (Fig. 2c) 1730cm 1 (Fe-(MA-(Bz-WF))) (Fig. 2d) in situ Fe-(MA-(Bz-WF)) 1.24T Fig. 2e-2g MA-WF Fe-(MA-WF) Bz- (Fe-(MA-WF)) FT-IR Fig. 2e 1730cm 1 MA-(Bz-WF) (Fig. 2c) WF Fig. 1 Examples of curves of magnetization (M) versus applied field (H). In superparamagnetism (SPM), the relevant material displays no remanence and coercivity phenomena, but with a saturation magnetization. Fig. 2 FT-IR spectra of (a) unmodified WF, (b) Bz-WF, (c) MA-(Bz-WF), (d) Fe-(MA-(Bz-WF)), (e) MA- WF, (f) Fe-(MA-WF), (g) Bz-(Fe-(MA-WF)), and (h) Fe-(CM-(Bz-WF)).
257 Fe-(MA-WF) Bz-(Fe-(MA-WF)) 1730cm 1 in situ (Fe-(MA-WF)) 1.83wt% Bz-(Fe-(MA-WF)) 0.54wt% Bz-(Fe- (MA-WF)) Fe-(MA-WF) in situ MA-WF MA-(Bz-WF) in situ Fig. 2g Fe-(CM-(Bz-WF)) FT-IR 1605cm 1 Fe-(CM-(Bz-WF)) 2.84wt% 3 2 WF in situ SQUID 100 298K Table 1 Fe-(MA-(Bz-WF)) WF in situ Fe-WF (PM) M vs H Bz-(Fe-(MA-WF)) Fe-(CM- (Bz-WF)) M vs H 298K (SPM) Fig. 3 nm 100K M vs H (FM) Langevin M s (298K) Bz-(Fe-(MA-WF)) Fe- (CM-(Bz-WF)) 0.47 2.32emu/g-sample Fe-(CM- (Bz-WF)) M s Fe-(CM-(HP- WF)) (M s = 3.11emu/g-sample) 7) Fig. 4 Bz-(Fe-(MA-WF)) Fe-(CM-(Bz-WF)) M vs T FC Fig. 3 Magnetization versus applied field curves for (a) Bz-(Fe-(MA-WF)) and (b) Fe-(CM-(Bz-WF)), measured at 100 and 298K. Inserts show the data on an enlarged scale. SPM ZFC (T max) M vs H (Fig. 3) 298K SPM Fig. 4a 4b Bz-(Fe- (MA-WF)) ZFC Fe-(CM-(Bz- WF)) Fe-(CM-(Bz-WF)) M vs H (Fig. 3b) (T B) Table 1 Fe-(CM-(Bz-WF)) T B = 20 27K 100K M vs H WF Fe-(CM-(Bz-WF)) WAXD WAXD Fig. 5 X PDXL
258 Fig. 5 WAXD intensity profiles for (a) Bz-(Fe-(MA- WF)) and (b) its hot-press molded sheet. Fig. 4 Temperature dependence of the magnetization in a field of 0.01 T for (a) Bz-(Fe-(MA-WF)) and (b) Fe-(CM-(Bz-WF)). The FC and ZFC plots were obtained for the sample with and without the field prior to the measurements, respectively. (δ -FeOOH) (Fe 3O 4) (γ -Fe 2O 3) Fe 3O 4 Fe-(CM-(Bz-WF)) Fe 3O 4 ( 121) Sherrer D (2) λ Cu X (CuKα 0.1542nm) β θ D 9.4nm SPM nm Fig. 6 as-prepared Fe-(CM-(Bz-WF)) 140 FE-SEM Bz-WF Fig. 6b 20 50nm SPM 100nm M vs T T B 100K 100K M vs H FM 3 3 (Bz-(Fe-(MA-WF)) Fe-(CM-(Bz-WF))) 140 7) Fe-(CM-(HP-WF)) 160 180 140 Table 1 Summary of the estimation of magnetic properties for modified WF samples.
12506(p.254-260) 13.3.18 12:08 ページ 259 259 木粉誘導体への酸化鉄ナノ微粒子の化学充填による超常磁性木質プラスチックの創製 レス前後では WAXD プロファイル (Fig. 5) に変化は無 く 磁化特性 (Table 1) もほぼ維持された Fig. 7 に 140 180 および 205 でのプレスにより得 たシートの写 真 を示 す Bz-(Fe-(MA-WF))(Fig. 7a)で は プレス温度によらず黄褐色で透明性を有するシート が得られた 既述の通り 酸化鉄 in situ 合成時のアル カリ処理の際にエステル加水分解が起こるために この 試料にはマレイン酸エステル基が含まれていない した がって 実質的に熱加工性の高い Bz-WF マトリックス中 に酸化鉄ナノ粒子が分散している状態ととらえられる 生成した酸化鉄粒子のサイズが十分に小さいため 可視 光の散乱が小さく 透明性を発現したものと考えられる 一方 Fe-(CM-(Bz-WF)) (Fig. 7b) を 140 でプレスし た場合には Fe3O4 に起因する赤褐色を呈する透明シー トが得られた しかしながら プレス温度の上昇と共に シートは黒変し不透明化する様子が観察された この黒 変は 酸化鉄ナノ微粒子がこの WF 誘導体内には Bz(Fe-(MA-WF))と比較して多く点在し過ぎることで熱流動 性が阻害され 分散性も低下することが一因と考えられ Fig. 6 FE-SEM images for the surfaces of (a) Bz-WF and (b) Fe-(CM-(Bz-WF)) sheets hot-pressed at 140. Scale bar denotes 500nm. る さらに Fe-(CM-(Bz-WF))シートに残存するカルボ キシル基によって マトリックスの有機成分が熱変性す ることによる可能性がある なお Fig. 7a に示すように 鉄含有率は相対的に低いものの酸官能基を含まない Bz(Fe-(MA-WF))では 205 でのプレスによってもこのよ うな黒変が生じる兆候はほとんど観られなかった Fig. 7c には 140 でプレスして得た Bz-(Fe-(MA-WF))シート が棒磁石に応答する様子を例示した 4 結 言 木粉 (WF) に熱可塑化と疎水化の目的でベンジル化を 施し アニオン性官能基の導入のためにマレイン酸エス テル化あるいはカルボキシメチル化を行った 次いで 得られた WF 誘導体を FeCl2 水溶液に浸漬し 鉄イオン をインターカレート吸着させた 洗浄後 1mol/L NaOH 水溶液に浸漬してアルカリ処理を行ってから過酸化水素 水による酸化処理を施し 酸化鉄を内包した WF 誘導体 を調製した エステル基を導入するとアルカリ処理時に加水分解さ れる傾向にあった アルカリに対して安定なベンジル基 およびカルボキシメチル基を導入して酸化鉄を内包させ た誘導体 Fe-(CM-(Bz-WF))は 140 で透明性を有する シートに成形でき そのシートは室温下で SPM を示し た FE-SEM 観察により 該シートには SPM を発現す る条件とされている数十 nm オーダーの酸化鉄ナノ微粒 子が点在していることが確認された なお 前報 7)の親 水性 WF 誘導体 ヒドロキシプロピル化 カルボキシル 化 WF をマトリックスとして酸化鉄の in situ 合成を施 したもの の成形可能な温度が 160 180 であったこ Fig. 7 Visual appearance of hot-pressed Bz-(Fe-(MAWF)) and Fe-(CM-(Bz-WF)) sheets transparent under an interior light (part a and b, respectively). Part c represents a Fe-(CM-(Bz-WF)) sheet (pressed at 140 ) responsive to a bar magnet. とから ベンジル化により熱可塑性はより高められたとい える また WF をマレイン酸エステル化し 先に酸化鉄 を内包させた後にベンジル化する工程によっても 良好な 成形加工性と室温 SPM を付与できることがわかった こ の最終誘導体 Bz-(Fe-(MA-WF))は Bz-WF に酸化鉄ナ
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