模具-注塑-手機充電器塑料模具,模具,注塑,手機充電器,塑料模具 FABRICATION OF PIEZOELECTRIC CERAMlClPOLYMER COMPOSITES BY INJECTION MOLDING. Leslie J. Bowen and Kenneth W. French, Materials Systems Inc. 53 Hillcrest Road, Concord, MA 01742 Abstract Research at the Materials Research Laboratory, Pennsylvania State University has demonstrated the potential for improving hydrophone performance using piezoelectric ceramic/polymer composites. As part of an ONR-funded initiative to develop cost-effective manufacturing technology for these composites, Materials Systems is pursuing an injection molding ceramic fabrication approach. This paper briefly overviews key features of the ceramic injection molding process, then describes the approach and methodology being used to fabricate PZT ceramic/polymer composites. Properties and applications of injection molded PZT ceramics are compared with conventionally processed material. Introduction Piezoelectric ceramic/polymer composites offer design versatility and performance advantages over both single phase ceramic and polymer piezoelectric materials in both sensing and actuating applications. These composites have found use in high resolution medical ultrasound as well as developmental Navy applications. Many composite configurations have been constructed and evaluated on a laboratory scale over the past thirteen years. One of the most successful combinations, designated 1-3 composite in Newnham’s notation [l 1, has a one-dimensionally connected ceramic phase (PZT fibers) contained within a three-dimensionally connected organic polymer phase. Hydrophone figures of merit for this composite can be made over 10,000 times greater than those of solid PZT ceramic by appropriately selecting the phase characteristics and composite structure. The Penn State composites were fabricated [l] by hand-aligning extruded PZT ceramic rods in a jig and encapsulating in epoxy resin, followed by slicing to the appropriate thickness and poling the ceramic. Aside from demonstrating the performance advantages of this material, the Penn State work highlighted the difficulties involved in fabricating 1-3 composites on a large scale, or even for prototype purposes. These are: 11 The requirement to align and support large numbers of PZT fibers during encapsulation by the polymer. 2) The high incidence of dielectric breakdown during poling arising from the significant probability of encountering one or more defective fibers in a typical large array. Over the past five years several attempts have been made to simplify the assembly process for 1-3 transducers with the intention of improving manufacturing viability and lowering the material cost. Early attempts involved dicing solid blocks of PZT ceramic into the desired configuration and back-filling the spaces with a polymer phase. This technique has found wide acceptance in the medical ultrasound industry for manufacturing high frequency transducers [2]. More recently, Fiber Materials Corp. has demonstrated the applicability of its weaving technology for fiber-reinforced composites to the assembly of piezoelectric composites [31. Another exploratory technique involves replicating porous fabrics having the appropriate connectivity [41. For extremely fine scale composites, fibers having diameters in the order of 25 to 100 pn and aspect ratios in excess of five are required to meet device performance objectives. As a result, these difficulties are compounded by the additional challenge of forming and handling extremely fine fibers in large quantities without defects. Recently, researchers at Siemens Corp. have shown that very fine scale composites can be produced by a fugitive mold technique. However, this method requires fabricating a new mold for every part [51. This paper describes a new approach to piezoelectric composite fabrication, viz: Ceramic injection molding. Ceramic injection molding is a cost- effective fabrication approach for both Navy piezoelectric ceramic/polymer composites and for the fabrication of ultrafine scale piezoelectric composites, such as those required for high frequency medical ultrasound and nondestructive evaluation. The injection molding process overcomes the difficulty of assembling oriented ceramic fibers into composite transducers by net-shape preforming ceramic fiber arrays. Aside from this advantage, the process makes possible the construction of composite transducers having more complex ceramic element geometries than those previously envisioned, leading to greater design flexibility for improved acoustic impedance matching and lateral mode cancellation. Process Descriotion Injection molding is widely used in the plastics industry as a means for rapid mass production of complex shapes at low cost. Its application to ceramics has been most successful for small cross- section shapes, e.g. thread guides, and large, complex shapes which do not require sintering to high density, such as turbine blade casting inserts. More recently, the process has been investigated as a production technology for heat-engine turbine components [6,71. The injection molding process used for PZT molding is shown schematically in Figure 1. By injecting a hot thermoplastic mixture of ceramic powder and organic binder into a cooled mold, complex shapes can be formed with the ease and rapidity normally associated with plastics molding. Precautions, such as hard-facing the metal contact surfaces, are important to minimize metallic contamination from the compounding and molding machinery. For ceramics, the binder must be removed nondestructively, necessitating high solids loading, careful control of the binder removal Powder Process i ng -r------ 4 CERAMIC PREFORM Organic Binder - - - - I Granulate I - - - - - - PREFORM LAY-UP TO FORM LARGER ARRAYS -_Lu-i_-- 1-1 and apply electrodes Figure 1 : Injection Molding Process Route. process, and proper fixturing. Once the binder is removed, the subsequent firing, poling and epoxy encapsulation processes are similar to those used for conventional PZTipolymer composites 11 I. Thus, the process offers the following advantages over alternative fabrication routes: Complex, near net-shape capability for handling many fibers simultaneously; rapid throughput (typically seconds per part); compatibility with statistical process control; low material waste; flexibility with respect to transducer design (allows variation in PZT element spacing and shape); and low cost in moderate to high volumes. In general, because of the high initial tooling cost, the ceramics injection molding process is best applied to complex-shaped components which require low cost in high volumes. Comoosite Fabrication and Evaluation The approach taken to fabricate 1-3 piezoelectric composites is shown in Figure 2a, which illustrates a PZT ceramic preform concept in which fiber positioning is achieved using a co-molded integral ceramic base. After polymer encapsulation the ceramic base is removed by grinding. Aside from easlng the handling of many fibers, this preform approach allows broad latitude in the selection of piezoelectric ceramic element geometry for composite performance optimization. Tool design is important for successful injection molding of piezoelectric composites. The approach shown in Figure 2b uses shaped tool inserts to allow changes in part design without incurring excessive retooling costs. Figure 2c shows how individual preforms are configured to form larger arrays. Figure 2a: Preform Configuration (Approx. 400 ceramic elements) REMOVABLE INSERT : CAVITY TOOL BODY U *SPRUE Figure 2b: Injection Molding Tool Configuration Figure 2c: Large Area Composite Arrays made from Preforms Figure 2: Preform Approach to Composite Fabrication. In practice, material and molding parameters must be optimized and integrated with injection molding tool design to realize intact preform ejection after molding. Key parameters include: PZT/binder ratio, PZT element diameter and taper, PZT base thickness, tool surface finish, and the molded part ejection mechanism design. In order to evaluate these process parameters without incurring excessive tool cost, a tool design having only two rows of 19 PZT elements each has been adopted for experimental purposes. Each row contains elements having three taper angles (0, 1 and 2 degrees) and two diameters (0.5 and lmm). To accommodate molding shrinkage, the size of the preform is maintained at 5Ox50mm to minimize the possibility of shearing off the outermost fibers during the cooling portion of the molding cycle. Figure 3: Injection Molded 1-3 Composite Preforms. 161 Figure 3 shows green ceramic preforms fabricated using this tool configuration. Note that all of the PZT elements ejected intact after molding, including those having no longitudinal tapering to facilitate ejection. Slow heating in air has been found to be a suitable method for organic binder removal. Finally, the burned-out preforms are sintered in a PbO- rich atmosphere to 97-98% of the theoretical density. No problems have been encountered with controlling the weight loss during sintering of these composite preforms, even for those fine-scale, high-surface area preforms which are intended for high frequency ultrasound. . .- . .. -. .. L. . Figure 4: Scanning Electron Micrographs of As-molded (Upper) and As-sintered (Lower) Surfaces of PZT Fibers. Figure 4 illustrates the surfaces of as-molded and as-sintered fibers, showing the presence of shallow fold lines approximately 10pm wide, which are characteristic of the injection molding process. The fibers exhibit minor grooving along their length due to ejection from the tool. Figure 5 shows the capability of near net-shape molding for fabricating very fine scale preforms; PZT element dimensions only 30pm wide have been demonstrated. The as-sintered surface of these elements indicates that the PZT ceramic microstructure is dense and uniform, consisting of equiaxed grains 2-3pm in diameter. Figure 5: Fine-scale 2-2 Composite formed by Near Net- shape Molding (Upper Micrograph). As-sintered Surface (Lower Micrograph). In order to demonstrate the lay-up approach for composite fabrication, composites of approximately 10 volume percent PZT-5H" fibers and Spurrs epoxy resin were fabricated by epoxy encapsulating laid-up pairs of injection molded and sintered fiber rows followed by grinding away the PZT ceramic stock used to mold the composite preform. Figure 6 shows composite samples made from freshly-compounded PZT/binder mixture and from reused material. Recycling of the compounded and molded material appears to be entirely feasible and results in greatly enhanced material utilization. Table 1 compares the piezoelectric and dielectric properties of injection molded PZT ceramic specimens with those reported for pressed PZT-5H samples prepared by the powder manufacturer. When the sintering conditions are optimized for the PZT-5H formulation, the piezoelectric and dielectric properties are comparable for both materials. Since the donor- doped PZT-5H formulation is expected to be particularly sensitive to iron contamination from the injection molding equipment, the implication of these measurements is that such contamination is negligible in this injection molded PZT material. *Powder supplied by Morgan Matroc, Inc., Bedford, Ohio; Lot 105A. 162 Table 1 : Properties of Injection Molded Piezoelectric Ceramics. Specimen Relative Dielectric d33 TY Pe Permittivity Loss (1 kHz1 (pC/N) Die-Pressed 3584 0.01 8 745 Inj. Molded** 3588 0.01 8 755 *Aged 24 hours before measuremegt. **Poling conditions: 2.4kV/mm, 60 C, 2 minutes. Figure 6: Injection Molded PZT Fiber/Epoxy Resin Composites prepared by the Preform Lay-up Method. Summarv Ceramic injection molding has been shown to be a viable process for fabricating both PZT ceramics and piezoelectric ceramic/polymer transducers. The electrical properties of injection molded PZT ceramics are comparable with those prepared by conventional powder pressing, with no evidence of deleterious effects from metallic contamination arising from contact with the compounding and molding equipment. By using ceramic injection molding to fabricate composite preforms, and then laying up the preforms to form larger composite arrays, an approach has been demonstrated for net-shape manufacturing of piezoelectric composite transducers in large quantities. Ac knowledaements This work was funded by the Office of Naval Research under the direction of Mr. Stephen E. Newfield. The authors wish to thank Ms. Hong Pham for technical assistance, and Dr. Thomas Shrout of the Materials Research Laboratory, Penn. State University for electrical measurements. References [l] R. E. Newnham et al, "Composite Piezoelectric Transducers," Materials in Engineering, Vol. 2, pp. 93-106, Dec. 1980. [21 C. Nakaya et al, IEEE Ultrasonics Symposium Proc., Oct. 16-18, 1985, p 634. 131 S. D. Darrah et al, "Large Area Piezoelectric Composites," Proc. of the ADPA Conference on Active Materials and Structures, Alexandria, Virginia, Nov. 4-8, 1991, Ed. G. Knowles, Institute of Physics Publishing, pp 139-142. A. Safari and D. J. Waller, "Fine Scale PZT Fiber/Polymer Composites, " presented at the ADPA Conference on Active Materials and Structures, Alexandria, Virginia, Nov. [41 4-8, 1991. [5] U. Bast, D. Cramer and A. Wolff, "A New Technique for the Production of Piezoelectric Composites with 1-3 Connectivity," Proc. of the 7th CIMTEC, Montecatini, Italy, June 24-30, 1990, Ed. P. Vincenzini, Elsevier, pp 2005-201 5. G. Bandyopadhyay and K. W. French, "Fabrication of Near-net Shape Silicon Nitride Parts for Engine Application," J. Eng. for Gas Turbines And Power, 108, J. Greim et al, "Injection Molded Sintered Turbocharger Rotors," Proc. 3rd. Int. Symp. on Ceramic Materials and Components for Heat Engines, Las Vegas, Nev., pp. 1365- 1375, Amer. Cer. Soc. 1989. [61 pp 536-539, 1986. 171 163 制作壓電陶瓷/聚合物復合注塑 萊斯利J. Bowen和肯尼思W.法國,材料Systems公司53 Hillcrest路,康科德,碩士01742 摘要 在材料研究實驗室,賓州州立大學研究已經證明改進水聽器表現(xiàn)的潛力使用壓電的制陶藝術/聚合物合成物. 為這些合成物,材料系統(tǒng)有成本效益的制造業(yè)技術正追求一制陶藝術的制造接近注射模塑. 本文簡要概述主要特征的陶瓷注塑成型工藝, 接著介紹的方式和方法可以被用來制造壓電陶瓷/聚合物復合材料. 性能和應用注塑壓電陶瓷與常規(guī)加工材料. 簡介 壓電的制陶藝術/聚合物合成物給予關于單相陶瓷和聚合物階段制陶藝術壓電的材料在遙感和實際應用兩方面設計多技能和表現(xiàn)優(yōu)勢。這些合成物已經在以及發(fā)展的海軍應用高分辨醫(yī)學超聲中找出使用. 在過去13年對許多實驗室進行了已建成組合配置和評價. 全球最成功的組合,指定1-3復合岡維爾的五線譜[l] 有一個連在尺寸上陶瓷相(壓電纖維)控制在一個三維連通有機高分子階段. 水聽器人物優(yōu)異這種復合材料可取得超過一萬倍以上的固體壓電陶瓷 由適當選擇的階段性特征和復合結構 在賓夕法尼亞州立復合材料[l]進行手工調擠壓壓電陶瓷棒在跳汰及封裝 環(huán)氧樹脂,然后切片到適當?shù)暮穸群蜆O化的陶瓷. 除了展現(xiàn)優(yōu)越的技術性能,這種材料, 在賓夕法尼亞州工作的突出困難,編造1-3復合材料的大規(guī)模 甚至為原型的目的. 這些措施包括: 1） 把許多的許多PZT纖維排成一排在包裝期間經過聚合物和支撐要求. 2） 2)在滑行期間電介質故障,起源于遭遇在一典型大陣列.中一根或更多有缺陷纖維的重要可能性的高發(fā)生. 過去五年已做了一些嘗試,以簡化裝配過程1-3傳感器與 有意提高制造業(yè)的可行性,并降低材料成本. 早期從事固體切丁塊壓電陶瓷成為理想的配置和回填土的空間內的一種高分子 相. 這項技術已廣泛接受了超聲醫(yī)學業(yè)生產高頻傳感器[2]. 最近, 纖維材料股份有限公司已證明適用其織造工藝纖維復合材料向大會壓電陶瓷復合材料 [3]. 另勘探技術涉及復制的多孔面料有適當?shù)倪B通[4]. 為極其好刻度合成物,纖維,大約25到100 pn和超過五一個尺寸與另一個尺寸之比有直徑需要來遭遇裝置表現(xiàn)目標. 因此,這些困難被附加挑戰(zhàn)用形成沒有缺點和處理在大數(shù)量中極其好纖維構成了. 最近,研究人員在西門子公司已表明很細尺度復合材料可以產生一個逃犯模具技術. 但是,這種方法需要制作一個新的模具,每部分[5]. 本文描述了一種新方法,壓電復合材料的制備,即:陶瓷注射成型. 陶瓷注射成型技術是一種有成本效益的制備方法雙方海軍的壓電陶瓷/聚合物復合材料的制備超細 規(guī)模壓電復合材料,例如那些需要高頻醫(yī)用超聲和無損評價. 注塑成型過程中,克服困難,裝配為主的陶瓷纖維復合成換用網(wǎng)狀預成型品陶瓷纖維 陣列. 除了這方面的優(yōu)勢, 這一進程使得有可能建造復合傳感器具有更復雜的陶瓷元件幾何比原先設想 導致更大的靈活性,設計為改進的聲阻抗匹配和橫向模式取消 加工工藝 注塑廣泛應用于塑料業(yè)作為一種手段,快速大量生產,形狀復雜,在 成本低. 應用陶瓷一直最成功的小型截面形狀,例如: 螺紋指南,及大型復雜形狀不需要燒結密度高,如渦輪葉片鑄造刀片. 最近,這一進程已展開調查,作為生產工藝熱發(fā)動機渦輪部件[6,7] 圖1:注射模塑過程路線. 注塑成型用于PZT成型見圖1. 注的熱點熱塑性混合陶瓷粉及有機結合成一個冷卻結晶 復雜的形狀,可以形成與方便與快捷通常與塑料成型. 防范措施,如硬面臨的金屬接觸面,這些都是重要的,以盡量減少金屬污染的加劇和成型機器. 陶瓷的粘結劑必須拆除非破壞性地,使成為必要高固體量,嚴格控制粘結劑,拆除過程中, 和正確裝夾. 一旦粘結劑是拆掉,隨后射擊 極化和環(huán)氧包封過程類似于常規(guī)pzti聚合物復合[1]. 因此,過程具有以下優(yōu)點替代加工路線:復雜 近凈形能力處理許多纖維同時發(fā)生; 快速吞吐量(通常每秒); 兼容性與統(tǒng)計過程控制; 低的材料浪費; 靈活應變傳感器設計(允許變化壓電元件間距和形狀); 成本低,在中度到高度卷. 總的來說,由于高的初始成本,工裝, 陶瓷注射成型是最好的應用復雜形狀零件需要低成本高產量 制造和評價 采取這種辦法,編造1-3壓電復合載在圖2a, 它說明了壓電陶瓷預制棒的概念,光纖定位是實現(xiàn)以共同塑造積分陶瓷基地. 聚合物后封裝在陶瓷拆除磨. 除了處理許多纖維 這預制棒做法使廣大緯度在選擇壓電陶瓷元件幾何形狀的綜合性能優(yōu)化. 工具的設計是成功的重要注塑壓電陶瓷復合材料. 辦法列于圖2b用途形工具刀片允許改變部分設計,又不過分更換工具成本. 圖2c顯示了個體預制棒配置,能夠形成較大的陣列 圖2:預制棒的方法綜合加工. 在實踐中, 材料成型參數(shù)必須優(yōu)化整合注塑模具設計實現(xiàn)完整的預制彈射后 成型. 關鍵參數(shù),包括:壓電/粘合劑比,壓電元件直徑和錐形,基地PZT的厚度,刀具表面光潔度, 而塑造的一部分彈射機制設計. 為了評價這些工藝參數(shù),又不過分工具成本 工具設計,僅有兩排19PZT的每一分子已經通過實驗目的. 每一行包含有三個 (0,1和2度)和兩個直徑(0.5lmm). 容納成型收縮, 大小坯維持在5ox50mm以盡量剪過的最外層纖維在 冷卻部分的成型周期. 圖3:注射塑造1-3混合成的預成型品. 圖3顯示綠色陶瓷預制裝配使用此工具配置. 看到所有的PZT分子趕出完好無損后成型,包括具有無縱一端漸漸變細變尖方便彈射. 慢熱空氣已被認為是一種合適的方法有機結合搬遷. 最后,燒出預制棒燒結在氣氛97-98%的理論密度. 沒有遇到任何問題與控制體重燒結過程中,這些組合坯 即使是這些優(yōu)秀的尺度,比表面積高預制棒是為高頻超聲波. 圖4:掃描電子顯微鏡對所塑造(上)以及燒結(下)面壓電纖維. 圖4說明了表面為成型和燒結纖維 顯示駐留淺褶皺系大約寬十所特征的注塑成型過程. 纖維呈現(xiàn)輕微開槽沿其長度,由于噴出的工具. 圖5顯示的能力近凈成型模具制作非常精細規(guī)模預制棒; 壓電元件尺寸只有30pm性已經顯現(xiàn). 等離子燒結面這些元素顯示了壓電陶瓷微觀結構致密,均勻. 為了展示裁員的辦法,為復合材料, 復合材料約10體積%了PZT-5H"纖維和spurrs環(huán)氧樹脂材料環(huán)氧灌封奠定了對 注塑成型及燒結纖維整齊之后磨走了壓電陶瓷股票用來塑造復合預制棒. f 5-26顯示復合材料制成的鮮混合pzt/粘合劑混合物和重用材料. 循環(huán)中的復雜化,并塑造材料似乎是完全可行的,結果大大提高材料的利用率 圖5:細2-2級復合材料組成的近余量成形(上顯微照片). 由于燒結面(下顯微照片). 為了展示裁員的辦法,為復合材料, 復合材料約10體積%了PZT-5H"纖維和環(huán)氧樹脂材料環(huán)氧灌封奠定了對 注塑成型及燒結纖維整齊之后磨走了壓電陶瓷股票用來塑造復合預制棒. f 5-26顯示復合材料制成的混合pzt/粘合劑混合物和重用材料. 循環(huán)中的復雜化,并塑造材料似乎是完全可行的,結果大大提高材料的利用率. 表1比較了壓電及介電性能的注塑壓電陶瓷標本所報道的壓了PZT-5H 樣品制備的粉末的廠商. 當燒結條件,適合了PZT-5H制定,壓電和介電性能比較兩種材料. PZT-5H制定預計將特別敏感鐵污染的注塑設備, 言下之意,這些測量是這種污染是微不足道,在這注塑壓電材料. 概要 陶瓷注射成型技術已被證明是一種可行的工藝制備兩種壓電陶瓷和壓電陶瓷/聚合物換能器. 電氣性能注塑壓電陶瓷媲美備傳統(tǒng)的粉末緊迫, 但沒有證據(jù)的有害影響來自金屬污染引起的接觸套匯和成型設備. 用陶瓷注塑造復合坯 然后打下了預制棒,形成較大復合陣列. 結束語 這項工作是由辦事處的海軍研究的指導下,斯蒂芬e.newfield. 作者要感謝洪女士范用于技術援助, 而威博士shrout的材料研究實驗室,西恩. 州立大學電氣測量. 參考文獻 [l] R. E. Newnham et al, "復合材料壓電換"材料工程卷, 2,pp. 93-106,1980年12月. [2] C. Nakaya et al, IEEE Ultrasonics Symposium Proc., Oct. 16-18, 1985, p 634 [3] S. D. Darrah,"大面積壓電復合材料",proc. 該adpa會議上活躍的材料和結構,弗吉尼亞州亞歷山,11月4日至8日,1991年版. g.knowles物理研究所出版,pp139-142. [4]A. Safari and D. J. Waller,"細尺度壓電纖維/高分子復合材料 "會上adpa會議上活躍的材料和結構,弗吉尼亞州亞歷山,11月4日至8日,1991年. [5] U. Bast, D. Cramer and A. Wolff,, "A New Technique for the Production of Piezoelectric Composites with 1-3 Connectivity," Proc. of the 7th CIMTEC, Montecatini, Italy, June 24-30, 1990, Ed. P. Vincenzini, Elsevier, pp 2005-201 5. [6] G. Bandyopadhyay and K. W. French,"Fabrication of Near-net Shape Silicon Nitride Parts for Engine Application," J. Eng. for Gas Turbines And Power, [7]J. Greim et al, "Injection Molded Sintered Turbocharger Rotors," Proc. 3rd. Int. Symp. on Ceramic Materials and Components for Heat Engines, Las Vegas, Nev., pp. 1365-1375, Amer. Cer. Soc. 1989