Highly electrophilic metallocenes and their role in alkene polymerizations

This summary explores three main topics: (1) zwitterionic alternatives to cationic metallocene alkyl complexes as olefin polymerization catalysts, based on borato (–BR ₃ ^- ) and boryl (–BR₂) substituted cyclopentadienyl ligands (R = C₆F₅); including zwitterionic zirconium allyl complexes of the type CpZr(η³-allyl){η³-allyl–CH₂B(C₆F₅)₃}; (2) reactions which contribute to catalyst deactivation, notably aluminum alkyl mediated C₆F₅ transfer reactions as well as C–H activation reactions including an unusual case of catalyst self-reactivation; (3) the role of highly electrophilic metallocene complexes of aluminum, zirconium and yttrium in combination with weakly coordinating anions as initiators for the carbocationic polymerization of isobutene and isobutene–isoprene copolymerizations is discussed. This revised version was published online in June 2006 with corrections to the Cover Date.     

Influence of different initiators on the adhesion properties of photopolymerized epoxides on gold and silicon

Photocuring of epoxides proceeds by a cationic mechanism. The required photoinitiators are iodonium or sulfonium salts with non-nucleophilic anions. The influence of different photoinitiators on the adhesion properties of both a rigid and a soft epoxide is examined. Depending on the substrates to be joined, different decomposition products of the initiators are concentrated in the interphase. This accumulation of decomposition products in the interphase leads to a decreased adhesion. On gold surfaces the sulfur of sulfonium salts is concentrated as expected. But surprisingly the iodine of the iodonium salts is also concentrated on gold. It could be shown by immobilization experiments that organic iodine compounds with the iodine in any oxidation state reacted with gold surfaces. Due to this reaction iodide anions are formed. On silicon surfaces the fluorine of the anions PF₆ ^- and SbF₆ ^- is concentrated due to the high affinity of silicon for fluorine. The iodonium salt with [B(C₆F₅)₄]anion contains no fluorine able to react with the silicon. Therefore, the fluorine cannot be concentrated in the interphase and the joints prepared with the soft epoxide containing this initiator have a higher shear strength compared to adhesives with conventional anions.     

Bimetallic nickel complexes of trimethyl phenyl linked salicylaldimine ligands: Synthesis, structure and their ethylene polymerization behaviors

Bimetallic salicylaldimine-nickel complexes, 2,4,6-Me₃-1,3-{[NCH–(3′-R-5′-Y-2′-O–C₆H₃)-κ²-N,O]Ni(Ph) (PPh₃)}₂ [R = tert-Bu, Y = Me, 1b; R = Ph, Y = H, 2b] were prepared and their catalytic behaviors of ethylene polymerization were investigated. The bimetallic complex 2b shows higher activities (2.9 × 10⁵ g PE mol⁻¹ Ni h⁻¹) for ethylene polymerization and affords polymer with high molecular weight (M_w = 1.41 × 10⁵) and broad molecular weight distribution (M_w/M_n = 6.1) than its mononuclear matrix, {[(2,6-Me₂C₆H₃)–NCH–(3′-Ph-2′-O–C₆H₃)-κ²-N,O]Ni(Ph)(PPh₃)} (3) (Activity = 5.5 × 10⁴ g PE mol⁻¹ Ni h⁻¹; M_w = 1.86 × 10⁴; M_w/M_n = 2.8).     

Syndiospecific styrene polymerization by (tert-BuC5H4)TiCl2(O-2,6-iPr2C6H3) – borate catalyst system

(^tBuC₅H₄)TiCl₂(O-2,6-ⁱPr₂C₆H₃) (2) exhibited relatively high catalytic activity for syndiospecific polymerization of styrene at 25 °C if both [PhMe₂NH]B(C₆F₅)₄ and a mixture of AlⁱBu₃/Al(n-C₈H₁₇)₃ were used as the cocatalyst. Effects of both organoaluminum and organoboron compounds were explored, and the effect of cocatalyst was different from that observed in 1-hexene polymerization catalyzed by Cp*TiCl₂(O-2,6-ⁱPr₂C₆H₃) (1). Resultant syndiotactic polystyrene possessed narrow molecular weight distribution under the optimized conditions, and the M_w values were unchanged during the time course.     

Developing a fulvene route to C1-bridged “constrained geometry” Ziegler catalyst systems

6-dimethylamino-6-methylfulvene (7) was converted to the [(C₅H₄)–CMe₂–NMe₂]⁻ ligand system (8) by treatment with methyllithium. Its reaction with MCl₄ (M = Zr, Ti) followed by treatment with CH₃Li gave the respective [(C₅H₄)–CMe₂–NMe₂]₂M(CH₃)₂ complexes (12). Their reaction with B(C₆F₅)₃ led to reactive metallocene cation complexes that instantaneously underwent CH activation at a N–CH₃ group to yield the metallacyclic cation complexes 15. (tert-butylaminomethyl)fluorene was prepared by the addition of tert-butylisocyanate to fluorenyllithium followed by hydride reduction. Deprotonation by a variety of bases gave rise to a series of competing and consecutive reactions to yield several unusually structured products, among them a fluorenyl-anellated η⁵-1-azapentadienyl anion equivalent (25) and [(flu)-CH₂–NCMe₃]Li₂ (23). An improved way of generating synthetically useful C₁-linked [Cp–C₁(R) _n –NR¹]^2- dianion equivalents was developed starting from 6-amino-6-methylfulvene (26). N-silylation followed by double deprotonation with, e.g., lithium diisopropylamide cleanly furnished the respective [(C₅H₄)–C(=CH₂)–NSiMe₃]^2- dianion 33 (isolated as the dilithio derivative). Its reaction with Cl₂Zr(NEt₂)₂ in THF gave [η⁵:κ-N-(C₅H₄)–C(=CH₂)–NSiMe₃]Zr(NEt₂)₂ 36. Activation of 36 with methylalumoxane in toluene led to the formation of a C₁-linked “constrained geometry” Ziegler catalyst that polymerized ethylene similarly as the [(C₅Me₄)SiMe₂NCMe₃]ZrCl₂ derived literature system. This revised version was published online in June 2006 with corrections to the Cover Date.     

Asymmetric 1,3‐Dipolar Cycloaddition Reaction between α,β‐Unsaturated Aldehydes and Nitrones Catalyzed by Well‐Defined Iridium or Rhodium Catalysts

Reaction of the complexes (S_M,R_C)‐[(η⁵‐C₅Me₅)M{(R)‐Prophos}(H₂O)](SbF₆)₂ (M=Rh, Ir) with α,β‐unsaturated aldehydes diastereoselectively gave complexes (S_M,R_C)‐[(η⁵‐C₅Me₅)M{(R)‐Prophos}(enal)](SbF₆)₂ which have been fully characterized, including an X‐ray molecular structure determination of the complex (S_Rh,R_C)‐[(η⁵‐C₅Me₅)Rh{(R)‐Prophos}(trans‐2‐methyl‐2‐pentenal)](SbF₆)₂. These enal complexes efficiently catalyze the enantioselective 1,3‐dipolar cycloaddition of the nitrones N‐benzylideneaniline N‐oxide and 3,4‐dihydroisoquinoline N‐oxide to the corresponding enals. Reactions occur with excellent regioselectivity, perfect endo selectivity and with enantiomeric excesses up to 94 %. The absolute configuration of the adduct 5‐methyl‐2,3‐diphenylisoxazolidine‐4‐carboxaldehyde was determined through its (R)‐(−)‐α‐methylbenzylamine derivative.     

Dynamic quenching of 5-(2′-ethyl-hexyloxy)-p-phenylene vinylene (MEH-PPV) by charge transfer to a C60 derivative in solution

The fluorescence of 5-(2′-ethyl-hexyloxy)-p-phenylene vinylene (MEH-PPV) quenched in solution in 1,2-dichlorobenzene by a soluble derivative of C₆₀ [1-(3-methoxycarbonyl)propyl-1-phenyl[6,6]C₆₁; [6,6]PCBM] is studied by changing the concentration of the quencher and by varying the temperature. For MEH-PPV and PCBM dissolved in 1,2-dichlorobenzene, the Stern–Volmer constant (K_SV) is 2 × 10³M⁻¹. At high temperature, K_SV is enhanced because thermal energy facilitates the diffusion of PCBM. The results show that dynamic quenching (rather than static quenching) is the basic mechanism. Comparison with data obtained from quenching studies of trans-stilbene indicates that a single acceptor in contact with an MEH-PPV macromolecule quenches the luminescence from hundreds of repeat units. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2553–2557, 2001     

Synthesis of novel biodegradable material poly(lactic acid-trimesic acid) via direct melt copolycondensation and its characterization

Directly starting from lactic acid (LA) and trimesic acid (TMA), novel biodegradable material poly(lactic acid-trimesic acid) (PLT), a modified polylactic acid (PLA) with terminal carboxyl, was synthesized via melt copolycondensation. The optimal synthetic conditions, including catalyst kinds and dosage, prepolymerization time, copolymerization temperature and time, were discussed. When L-lactic acid (L-LA) and TMA as molar feed ratio n(L-LA)/n(TMA) 120/1 was prepolymerized for 8 h at 140 °C, the copolycondensation catalyzed by 0.9 wt % SnCl₂ at 190 °C for 8 h gave PLT with the biggest intrinsic viscosity ([η]) 1.91 dL∙g⁻¹, and the corresponding weight-average molecular weight (M_w) was 14,100 Da. Serial L-PLTs at different molar feed ratios were synthesized and characterized with FTIR, ¹H NMR, GPC, DSC, and XRD. Increasing n(L-LA), M_w increased first, and the biggest M_w was 17500 Da at n(L-LA)/ n(TMA) 240/1, then decreased. Using D,L-lactic acid (D,L-LA) instead of L-LA, the influences of LA stereochemical configuration were investigated. The peak phenomenon of M_w was similar, but the biggest M_w was 23,100 Da at n(D,L-LA)/n(TMA) 320/1. The serial L-PLTs had a certain crystallinity (10.2%∼23.0%), while all D,L-PLTs were amorphous. These differences may be in touch with the reaction mechanism of direct melt copolycondensation. The method was simple and practical for the synthesis of PLA biomedical materials applied in drug delivery carrier, and vessel substitution material.     

Enhanced Hydrogenation Activity and Recycling of Cationic Rhodium Diphosphine Complexes through the Use of Highly Fluorous and Weakly‐Coordinating Tetraphenylborate Anions

The effect of the nature of the anion on the performance of ionic rhodium catalysts has received little attention. Herein it is shown that the use of highly fluorous tetraphenylborate anions can enhance catalyst activity in both conventional and fluorous media. For hydrogenation catalysts of the type [Rh(COD)(dppb)][X] {COD=1,5‐cis,cis‐cyclooctadiene; dppb=1,4‐bis(diphenylphosphino)butane; X=BF₄⁻ ( 1a ), [BPh₄]⁻ ( 1b ), [B{C₆H₄(SiMe₃)‐4}₄]⁻ ( 1c ), [B{C₆H₃(CF₃)₂‐3,5}₄]⁻ ( 1d ), [B{C₆H₄(SiMe₂CH₂CH₂C₆F₁₃)‐4}₄]⁻ ( 1e ), [B{C₆H₄(C₆F₁₃)‐4}₄]⁻ ( 1f ) and [B{C₆H₃(C₆F₁₃)₂‐3,5}₄]⁻ ( 1 g )} the activity towards the hydrogenation of 1‐octene in acetone increased in the order 1c < 1b < 1e < 1a < 1d ~ 1f < 1g with 1g being twice as active as the commonly applied 1a . Despite the fluorophilic character introduced by the substituted tetraarylborate anions, the presence of some perfluoroalkyl‐substituents in the cation was still required for achieving high partition coefficients. Therefore, [Rh(COD)(Ar₂PCH₂CH₂PAr₂)][X] {Ar=C₆H₄(SiMe₂CH₂CH₂C₆F₁₃)‐4, X=[B{C₆H₃(C₆F₁₃)₂‐3,5}₄]⁻ ( 3f ); Ar=C₆H₄(SiMe(CH₂CH₂C₆F₁₃)₂)‐4 and X=[B{C₆H₄(C₆F₁₃)‐4}₄]⁻ ( 2g )} were prepared, which were active in the hydrogenation of 1‐octene, 2g even more so than 3f . Both these highly fluorous catalysts could be recycled with 99% efficiency through fluorous biphasic separation, whereas the corresponding BF₄⁻ complex of 2g ( 2a ) did not show any affinity for the fluorous phase.     

Enthalpies of vaporization of oligomers of poly(hexamethylene sebacate) and esters of alkylcarboxylic acids

Enthalpies of vaporization for esters covering a molecular weight range of about 74–939 g/mol · [monocarboxylics; linear esters of sebacic series; branched esters of triglyceride series; and, oligomer esters of poly(hexamethylene sebacate)] and a temperature range of about 273.15–523.15 K have been empirically fitted to within about 5% to an equation of the following form: ΔHv(T,M) = S(T)f(M) + I₀(T), where S(T) = C Ln(T) + K₀, I₀(T) = aT + b₀, and f(M) = M/(1 + a₀M), M is the molecular weight (molar mass); T is in degrees Kelvin; and, C, K₀, a, b₀, and a₀ are constants. These results were used to determine the heat capacity difference, ΔC_p = C_p(l) − C_p(g), and compared to calculated values from functional relationships of C_p(l) and C_p(g), l is liquid g is gas. The heat capacity difference results in conjunction with C_p(l) were used to empirically calculate the heat capacity of the gas, C_p(g), over the molecular weight and temperature ranges investigated and compared to a group contribution method. The functional forms for ΔHv(T,M), ΔC_p(T,M), C_p(l), and C_p(g) were also found to be applicable for n-alkanes. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 731–746, 1998     

Polymerized Surfactant Vesicles

Irradiation of surfactant vesicles prepared from (C₁₈H₃₇)₂ N⁺(CH₃)C₆H₄-CHCH₂p,CT⁻, 1, [C₁₅H₃₁CO₂(CH₂)₂]₂N⁺(CH₃)CH₂C₆H₄CHCH₂,CL⁻ 2, and (C₁₈-H₃₇)₂N⁺(CH₃)CH₂CH₂OCOC₆H₄CHCH₂p,Br⁻, 3, by ultraviolet light or by bursts of 266 nm laser pulses have resulted in the loss of styrene absorbances. This process has been accounted for in terms of a model which considers intravesicular surface reactions to give polymers with average chainlength of 22. Degreees of photopolymerization have been determined in vesicles prepared from 3 subsequent to separating the polystryrene, formed in the photolysis, from the surfactants. Vesicle surface photopolymerizations result in aqueous cleft formation and in enhanced stabilities. Polymerized vesicles provide media for in situ generation of colloidal catalysts and semiconductors.     

Synthesis and Properties of Novel Phenylenediamine Gemini Surfactants

In the present work, a two-step method was adopted to synthesize a series of novel Gemini surfactants using N,N-dimethylalkyl amines (alkyl length = C₁₂, C₁₆ and C₁₈), epichlorohydrin, and n-phenyllenediamine as starting materials. The products were characterized using mass spectroscopy (MS) and nuclear magnetic resonance spectroscopy (¹H NMR). Systematic experiments were conducted to evaluate their surface activity, foaming properties, and antibacterial performance. Results showed the critical micelle concentrations (CMC) of the C₁₂-based, C₁₆-based, and C₁₈-based phenylenediamine surfactants were 3.295 × 10⁻³, 2.532 × 10⁻⁴, and 3.140 × 10⁻⁴ mol L⁻¹ at 298 K, respectively, with corresponding surface tension (γ_cmc) values of 28.24, 31.95, and 35.06 mN m⁻¹ under the same conditions. The Gemini surfactants showed not only good surface activity and foaming properties, but also demonstrated good antimicrobial performance against Gram-positive and Gram-negative bacteria and fungi.     

General aspects of ethylene polymerization by d0 and d0f n transition metals

We present a generalized view of d⁰and d⁰f ⁿ metal complexes as olefin polymerization catalysts from computational studies of the {L}M–C₂H₅ ^(0,+,2+)-fragments (M = Sc(III), Y(III), La(III), Lu(III), Ti(IV), Zr(IV), Hf(IV), Ce(IV), Th(IV) and V(V); L = NH–(CH)₂–NH^2- {1}, N(BH₂)–(CH)₂–(BH₂)N^2- {2}, O–(CH)₃–O^- {3}, Cp₂ ^2- {4}, NH–Si(H₂)–C₅H₄ ^2- {5}, {(oxo)(O–(CH)₃–O)}^3- {6}, (NH₂)₂ ^2- {7}, (OH)₂ ^2- {8}, (CH₃)₂ ^2- {9}, NH–(CH₂)₃–NH^2- {10} and O–(CH₂)₃–O^2- {11}). This revised version was published online in June 2006 with corrections to the Cover Date.     

Development of the Eco-Cascade- cell reactor

The development of multicompartment rotating cylinder electrode reactors for the removal of metal from aqueous solutions is described. Such reactors approximate to a cascade of continuously stirred tank reactors and the results illustrate that, for electrodeposition of copper powder from acid sulphate solutions, high overall conversions (about 98%) may be realised, with low exit metal concentrations (about 1 mg dm^–3) and reasonable current efficiencies (65–87%).Nomenclature A electroactive surface area (cm²) - C _in inlet concentration of metal (mg dm^–3) - C _out outlet concentration of metal (mg dm^–3) - C _reactor reactor concentration of metal (mg dm^–3) - f _R fractional conversion - (f _R)n overall fractional conversion - F Faraday=96 500 (C mol^–1) - I _L limiting current (A) - k _l mass transfer coefficient (cms^–1) - m weight of metal (g) - M molecular weight of metal - n number of reactor elements in the cascade - N volumetric flow rate (cm³ s^–1) - z electron change - dm/dt rate of removal of metal (gs^–1) This paper was presented, in part, at the Electrochemical Reaction Engineering Symposium, Southampton University, April (1979).     

Interesting Copper(I) Coordination Polymers of Heterocyclic Monothioether Ligand Containing Long S-Hexadecyl Chain: Syntheses,Structures and Properties

Two structurally related heterocyclic monothioether ligands containing long S-alkyl(hexadecyl) chain, 2-methyl-5-(1-n-hexadecylsulfanyl)-1,3,4-thiadiazole (L ¹ ) and 2-(1-n-hexadecylsulfanyl) pyridine (L ² ), have been designed, and two CuI complexes with these ligands, [Cu₄I₄(L¹)₂] _n (1) and [Cu₄I₄(L²)₂] _n (2), have been synthesized and characterized by IR, elemental analysis, UV–vis spectra, thermal analysis and X-ray diffraction analysis. Single-crystal X-ray analyses show that two complexes are all 1-D coordination polymer with a double-stranded stair CuI-chain. Optical diffuse-reflection spectra results complex 1 and 2 have the properties of the semiconductor.     

Photoinitiated cationic polymerization of urethane vinyl ether crystalline monomers

Photoinitiated cationic polymerization of crystalline monomers based on urethane vinyl ether has been investigated by means of differential photocalorimetry (DPC). The crystalline monomers in the melt state polymerized rapidly by exposure to UV light in the presence of a cationic photoinitiator such as an iodonium salt, sulfonium salt or iron arene salt. The kinetics of the cationic photopolymerization process were studied by following k_p[M⁺] as a function of conversion. High conversions, of around 90 %, were obtained for most of the systems investigated. The efficiency of the cationic photoinitiators in initiating the polymerization of the vinyl ether monomers was in the order: iodonium salt > iron arene salt > sulfonium salt. Monomers modified with different saturated alcohols had different activities in photopolymerization, although they all carry the same functional group, i.e. vinyl ether. Copyright © 2005 Society of Chemical Industry     

Grain-orientated lead-free BNT-based piezoceramics with giant electrostrictive effect

In this study, we propose an effective approach to gain prominent electrostrictive behavior by taking advantage of texture construction in lead-free (Bi_0.5Na_0.5)TiO₃(BNT)-based piezoceramics for actuator applications. The electrostrictive effect was explored systematically in <00 l> textured 0.90(0.83Bi_0.5Na_0.5TiO_3-0.17Bi_0.5K_0.5TiO₃)-0.10NaNbO₃(BNT-BKT-NN) ceramics with respect to grain orientation, temperature and electric fields. It was found that the electrostrctive coefficient Q₃₃ and recoverable strain increase monotonously with the grain orientation increasing. At the optimized microstructure (F_00 l=92%), a giant Q₃₃ with nearly purely electrostrictive characteristics was detected to be around ~0.0354 m⁴C⁻², which was far larger than the reported values of Pb(Mg_1/3Nb_2/3)O₃ (PMN) and the existing BNT-based electrostrictive materials. Meanwhile, the acquired Q₃₃ was found to exhibit excellent stability for the highly textured sample under different temperature or electric field conditions. Our achievement demonstrates that the giant electrostrictive properties with superior temperature and electric field stability for <00 l> textured BNT-BKT-NN ceramic are of great significance in replacing traditional PMN ceramics for actuator applications.     

Treatment of wastewaters from the olive mill industry by sonication

BACKGROUND: In this study, the effects of additives (manganese (III) oxide (Mn₃O₄), Cu⁺², Fe⁰ and potassium iodate (KIO₃)) and radical scavengers (sodium carbonate (Na₂CO₃), perfluorohexane (C₆F₁₄) and t‐buthyl alcohol (C₄H₁₀O)) on the dephenolization, decolorization, dearomatization and detoxification of olive mill wastewater (OMW) by sonication were investigated because wastewaters from this industry are not removed effectively. RESULTS: The maximum COD, color, total phenol and total aromatic amines (TAAs) removal efficiencies were 63, 82, 78 and 71%, respectively, at 60 °C with sonication only. The TAAs and phenol yields were increased to 96 and 97% with 6 mg L^?1 KIO₃ and 3 mg L^?1 Fe⁰ while color removal reached 97% with 6 mg L^?1 C₆F_14. The total annual cost with sonication only was 665 € m^?3 year^?1 while the cost slightly increased (666€ m³ year^?1) with C₆F₁₄. The maximum acute toxicity removals were 97‐98% in Daphnia magna and Vibrio fischeri The Microtox acute toxicity test was more sensitive than the Daphnia magna to the OMW samples. CONCLUSION: COD, color, total phenol, TAAs and toxicity in an OMW were removed efficiently and cost‐effectively by sonication. © 2012 Society of Chemical Industry     

Mass transfer characteristics and overall mass transfer coefficient in the ozone contactor

The overall mass transfer coefficient k_La,F in the flow characteristics was determined by the measurement of the diffusivity of ozone, density of aqueous solution, and viscosity. However, the measured values k_La,F in the range of 0.0096–0.0622 min^-1 show large changes in hydraulic retention time, and the dissolved ozone concentration C_L,F presented under 0.1 mg/l is lower than the dissolved ozone observed. The overall mass transfer coefficient k_La,M in the ozone decomposition was determined by measurement of the equilibrium dissolved ozone, overall decomposition rate constant, and overall Henry’s law constant. The measured values k_La,M are in the range of 0.0441–0.0749 min^-1, and they present small changes depending on the hydraulic retention time. Furthermore, the measured dissolved ozone concentration C_L,M presents a larger value than the C_L,F. Then, the k_La,M is selected as an input overall mass transfer coefficient to predict the dissolved ozone requirement in the ozone contactor.     

Significantly enhanced pyroelectric performance in novel sodium niobate-based lead-free ceramics by compositional tuning

In this study, (1 − x)NaNbO₃–xBa_0.6(Bi_0.5K_0.5)_0.4TiO₃ (abbreviated as NN-xBBKT, x = 0.05, 0.10, 0.15, and 0.20) lead-free pyroelectric ceramics were synthesized by conventional solid-state reaction method. Moreover, their microstructure, phase structure, dielectric, ferroelectric, piezoelectric, and pyroelectric characteristics were studied systematically. The X-ray diffraction result showed that the phase structure of NN-xBBKT ceramics changed from orthorhombic to tetragonal and finally became pseudocubic symmetry. The ferroelectric-paraelectric phase transition temperature and depolarization temperature shifted to lower temperature with the increase in BBKT content. Furthermore, with increasing BBKT content, piezoelectric coefficient, figures of merit, and pyroelectric coefficient first increased and then decreased. The optimum pyroelectric properties (eg F_d = 0.81 × 10⁻⁵ Pa^−1/2, F_v = 1.02 × 10⁻² m² C⁻¹, F_i = 1.04 × 10⁻¹⁰ m V⁻¹, and p = 3.11 × 10⁻⁸ C cm⁻² K⁻¹) were observed in sample composition with x = 0.15. More importantly, the pyroelectric coefficient of ceramic with x = 0.15 also displayed relatively high thermal stability because of high depolarization temperature (~110°C). These parameters demonstrate that the novel Pb-free NaNbO₃-based ceramics form an important class of pyroelectric material with broad range of application prospect.