本文選題：復(fù)合材料　切入點(diǎn)：酚醛樹脂　出處：《中國林業(yè)科學(xué)研究院》2012年博士論文

【摘要】：鋁木復(fù)合裝飾板是一種新型的復(fù)合材料，作為高檔裝飾板在我國起步較晚。鋁箔貼面人造板具有優(yōu)良的裝飾性、防水防潮、耐磨抗龜裂、隔熱阻燃等性能，廣泛應(yīng)用于建筑裝飾裝修、家具裝飾裝修和車輛裝飾裝修的高檔裝飾材料。由于木材和鋁材是兩種表面極性不同的材料，因此，鋁木復(fù)合制備裝飾板需要使用價格較貴、經(jīng)過改性的特殊膠黏劑，且粘接材料表面處理和熱壓復(fù)合工藝復(fù)雜。因此，本文通過酚醛樹脂改性，篩選價格低廉、性能優(yōu)良的改性酚醛樹脂膠黏劑，優(yōu)化改性酚醛樹脂（PF）膠黏劑熱壓制備鋁木復(fù)合裝飾人造板制備工，探討鋁木復(fù)合機(jī)理研究。 本文詳細(xì)研究了不同改性酚醛樹脂熱壓制備復(fù)合材料的性能，確定了聚乙酸乙烯酯乳液（PVAc）改性酚醛樹脂方法；采用正交試驗(yàn)設(shè)計(jì)和單因素試驗(yàn)設(shè)計(jì)，系統(tǒng)研究了鋁木復(fù)合熱壓工藝和參數(shù)，以及酚醛樹脂與聚乙酸乙烯酯乳液不同混合比例及添加偶聯(lián)劑對復(fù)合裝飾板性能的影響；通過利用接觸角測定儀、傅里葉紅外變換光譜（FT-IR）和反射光譜（RA-IR）、掃面電子顯微鏡（SEM）和X射線光電子能譜（XPS）等儀器，對鋁箔表面臨界自由能、材料表面與界面形貌特征、鋁木復(fù)合配位鍵等進(jìn)行測試和分析，探討了鋁木復(fù)合材料材料界面性能和鋁木復(fù)合機(jī)理，為鋁/木復(fù)合材料的制備和創(chuàng)新性應(yīng)用提供理論基礎(chǔ)，推動鋁/木復(fù)合材料在室內(nèi)裝飾裝修和家具中的應(yīng)用，促進(jìn)木材工業(yè)的技術(shù)進(jìn)步，為產(chǎn)業(yè)結(jié)構(gòu)調(diào)整提供技術(shù)支撐。具體研究結(jié)果如下： （1）聚乙烯醇縮丁醛（PVB）、聚乙酸乙烯酯乳液等熱塑性樹脂改性酚醛樹脂為膠黏劑熱壓制備鋁木復(fù)合裝飾板。性能測試表明：聚乙酸乙烯酯乳液改性酚醛樹脂膠黏劑制備的鋁箔貼面纖維板，表面膠合強(qiáng)度最高，為1.36MPa，具有良好的浸漬剝離性能，選定聚乙酸乙烯酯乳液改性酚醛樹脂作為熱壓制備鋁木復(fù)合裝飾板膠黏劑。 （2）采用正交實(shí)驗(yàn)設(shè)計(jì)對聚乙酸乙烯酯乳液改性酚醛樹脂制備鋁木復(fù)合材料熱壓工藝進(jìn)行研究，探討熱壓溫度、熱壓時間、熱壓壓力和施膠量等熱壓因素對復(fù)合材料物理力學(xué)性能的影響。研究結(jié)果表明：熱壓溫度對產(chǎn)品的各項(xiàng)性能指標(biāo)影響極顯著，熱壓工藝因素主次順序?yàn)闊釅簻囟葻釅簳r間熱壓壓力施膠量。極差分析結(jié)果表明，優(yōu)化熱壓工藝為：熱壓溫度140℃，熱壓時間9min，熱壓壓力0.6MPa，施膠量200g/m2。 （3）采用酚醛樹脂與聚乙酸乙烯酯乳液不同混合比例配置的膠黏劑，熱壓制備的鋁箔貼面人造板表面膠合強(qiáng)度都超過1.0MPa。酚醛樹脂與聚乙酸乙烯酯乳液不同混合比對以楊木單板為基材的鋁箔貼面人造板的表面膠合強(qiáng)度影響極顯著，對以中密度纖維板為基材的鋁箔貼面人造板表面膠合強(qiáng)度影響不顯著；以楊木單板為基材的酚醛樹脂與聚乙酸乙烯酯乳液最佳混合比為2：1，以中密度纖維板為基材的酚醛樹脂與聚乙酸乙烯酯乳液最佳混合比為1：1。偶聯(lián)劑添加到酚醛樹脂中提高了復(fù)合裝飾板的表面膠合強(qiáng)度和浸漬剝離性能。 （4）鋁木復(fù)合裝飾板與中密度纖維板相比，無法形成燃燒。熱釋放速率峰值（pkHRR）、平均熱釋放速率（Avg-HRR）、有效燃燒熱（EHC）和熱釋放總量（THR）分別下降了97.3%、98.3%、90.6%和96.6%，但總釋煙量（TSR）和殘重率（Mass）卻增加716%和331.9%。鋁木復(fù)合裝飾板CO、CO_2的質(zhì)量分?jǐn)?shù)都很低，有效的降低了有害氣體的釋放。 （5）鋁箔表面經(jīng)打磨、打磨加水洗處理后，表面臨界自由能提高了2倍和4倍，潤濕性增強(qiáng)。SEM結(jié)果顯示，改性酚醛樹脂膠黏劑都能夠充分潤濕鋁箔表面，形成連續(xù)的膠層；膠黏劑滲透到基材空隙中形成膠釘，產(chǎn)生機(jī)械力。 （6）固化酚醛樹脂、聚乙酸乙烯酯乳液、改性酚醛樹脂膠黏劑紅外吸收光譜中，存在較強(qiáng)的羥基吸收峰，在鋁箔表面固化的酚醛樹脂、聚乙酸乙烯酯乳液、改性酚醛樹脂紅外反射吸收光譜中，羥基吸收峰檢測不到，表明樹脂中的羥基與鋁表面形成化學(xué)結(jié)合；聚乙酸乙烯乳液、改性酚醛樹脂紅外反射吸收光譜中的羰基向高峰區(qū)偏移，表明酯基中的碳氧鍵與鋁箔表面形成配位鍵。 （7）在鋁箔表面固化的聚乙酸乙烯酯乳液改性酚醛樹脂XPS圖譜分析表明：鋁箔表面存在鋁的金屬態(tài)和氧化態(tài)兩種形式；碳和氧的結(jié)合能向高位區(qū)移動，存在多個配位的C1s和O1s峰，表明改性酚醛樹脂中的氧和鋁表面形成配位鍵，產(chǎn)生化學(xué)結(jié)合，，膠合強(qiáng)度提高。
[Abstract]:Aluminum wood composite decorative board is a new type of composite material, as a high-end decorative plate starts late in our country. Aluminum foil veneer artificial board with decorative, excellent waterproof, wear-resistant anti cracking, thermal insulation flame retardant properties, widely used in building decoration, furniture decoration and vehicle decoration of high-grade decorative materials because wood and aluminum are two different surface polarity material, therefore, the preparation of aluminum wood composite decorative board need to use expensive, after special adhesive modification, surface treatment and adhesive materials and composites complex. Therefore, the modified phenolic resins, screening of low price, phenolic modified resin adhesive with excellent performance, optimization of modified phenolic resin adhesive (PF) was fabricated by hot pressing aluminum wood composite decorative board fabrication, study on Mechanism of aluminum composite wood.
In this paper, the different properties of the composites by hot pressing of phenolic resin was studied in detail, the polyvinyl acetate emulsion (PVAc) modified phenolic resin method; orthogonal experiment design and single factor experimental design, system of aluminum wood composite hot pressing process and parameters, and phenolic resin and polyvinyl acetate emulsion mixed proportion and adding coupling agent on the properties of the composite decorative board; by using contact angle measurement, Fourier transform infrared spectroscopy (FT-IR) and reflection spectra (RA-IR), scanning electron microscopy (SEM) and X ray photoelectron spectroscopy (XPS) and other instruments on aluminum foil surface critical free energy surface with the interface morphology, aluminum composite wood coordination bond test and analysis, discusses the aluminum wood composite material interface properties and mechanism of aluminum composite wood, aluminium / wood composite material preparation and innovative applications The theoretical basis is to promote the application of aluminum / wood composites in interior decoration and furniture, promote the technological progress of wood industry, and provide technical support for the adjustment of industrial structure.
(1) polyvinyl butyral (PVB), polyvinyl acetate emulsion thermoplastic resin modified phenolic resin as adhesive was fabricated by hot pressing aluminum wood composite decorative board. The performance tests show that the polyvinyl acetate emulsion modified aluminum foil veneer fiber board of phenolic resin adhesive preparation, surface bonding strength is 1.36MPa, the highest. With immersion good performance, selected the polyvinyl acetate emulsion modified phenolic resin as the hot pressing preparation of aluminum wood composite decorative plate adhesive.
(2) by using the orthogonal experimental design of polyvinyl acetate emulsion modified phenolic resin prepared by hot pressing aluminum wood composite materials technology research of hot pressing temperature, hot pressing time, hot pressing pressure and sizing of hot pressing factors on the physical and mechanical properties of composite materials. The results showed that the effect of hot pressing temperature on the performance of index of the product is very significant, hot pressing factors for hot pressing time hot pressing temperature pressure sizing. The analysis results showed that the optimum hot pressing for the hot pressing temperature is 140 degrees centigrade, hot pressing time 9min, pressure 0.6MPa, size 200g/m2.
(3) using adhesive phenolic resin and polyvinyl acetate emulsion with different mixing ratio configuration, significant effect of 1.0MPa. phenolic resin and polyvinyl acetate emulsion surface bonding strength of different mixing ratio on poplar veneer as substrate made of aluminum foil foil stickers dough plate facing artificial plate surface bonding strength of hot pressing preparation are more than for, from MDF for aluminum foil veneer glued board surface strength effect of substrate is not significant; with the poplar veneer as substrate with phenolic resin polyvinyl acetate emulsion the best mixing ratio is 2:1, the MDF substrate for phenolic resin and polyvinyl acetate emulsion the best mixing ratio is 1:1. the coupling agent is added to the improved phenolic resin composite decorative board surface bonding strength and peeling performance.
(4) aluminum wood composite decorative plate compared with the MDF, unable to form combustion. The peak heat release rate (pkHRR), the average heat release rate (Avg-HRR), effective heat of combustion (EHC) and total heat release (THR) were decreased by 97.3%, 98.3%, 90.6% and 96.6%, but the total smoke release amount (TSR) and residual rate (Mass) was increased by 716% and 331.9%. aluminum wood composite decorative plate CO, the mass fraction of CO_2 is very low, effectively reduce the release of harmful gases.
(5) aluminum foil surface after polishing, polishing water washing treatment, the surface of critical free energy increased by 2 times and 4 times the wettability.SEM results showed that the modified phenolic resin adhesive can be fully wetting aluminum foil surface to form a continuous layer; adhesive glue nail penetration into the substrate gap, produce mechanical power.
(6) curing phenolic resin, polyvinyl acetate emulsion, modified phenolic resin adhesive in the infrared absorption spectrum, there is a strong absorption peak of hydroxyl in phenolic resin, curing the surface of aluminum foil, polyvinyl acetate emulsion, modified phenolic resin, infrared reflection absorption spectroscopy, hydroxyl absorption peak was not detected, suggesting that the hydroxyl and the aluminum surface in the resin forming chemical bond; poly vinyl acetate emulsion modified phenolic resin, infrared reflection absorption spectra in the carbonyl offset to the peak area, showed that the ester group in the carbon oxygen bond and surface form coordination bonds.
(7) in curing surface of aluminum foil polyvinyl acetate emulsion modified phenolic resin XPS spectra analysis indicates that there are metal state and the oxidation state of two kinds of aluminum foil surface; combination of carbon and oxygen can move to the high area, there are a number of ligands C1s and O1s peak, showed the modified phenolic resin the oxygen and aluminum surface to form coordination bonds, chemical bonding, the bonding strength increased.

【學(xué)位授予單位】：中國林業(yè)科學(xué)研究院
【學(xué)位級別】：博士
【學(xué)位授予年份】：2012
【分類號】：TS653.3

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