Proc. Nadl. Acad. Sci. USAVol. 89, pp. 821-826, February 1992Colloquium Paper

This paper was presented at a colloquium entitled "Industrial Ecology," organized by C. Kumar N. Patel, held May20 and 21, 1991, at the National Academy of Sciences, Washington, DC.

Alternative starting materials for industrial processes(replacement chemicals/toxic reagent substitutes/on-demand chemical generation)

JAMES W. MITCHELLAnalytical Chemistry Research Department, AT&T Bell Laboratories, Murray Hill, NJ 07974

ABSTRACT In the manufacture of chemical feedstocksand subsequent processing into derivatives and materials, theU.S. chemical industry sets the current standard of excellencefor technological competitiveness. This world-class leadershipis attributed to the innovation and advancement of chemicalengineering process technology. Whether this status is sus-tained over the next decade depends strongly on meetingincreasingly demanding challenges stimulated by growing con-cerns about the safe production and use of chemicals withoutharmful impacts on the environment. To comply with stringentenvironmental regulations while remaining economically com-petitive, industry must exploit alternative benn starting ma-terials and develop environmentally neutral industrial pro-cesses. Opportunities are described for development of envi-ronmentally compatible alternatives and substitutes for some ofthe most abundantly produced, potentially hazardous indus-trial chemicals now labeled as "high-priority toxic chemicals."For several other uniquely important commodity chemicalswhere no economically competitive, environmentally satisfac-tory, nontoxic alternative starting material exists, we advocatethe development of new dynamic processes for the on-demandgeneration of toxic chemicals. In this general concept, whichobviates mass storage and transportation of chemicals, toxicraw materials are produced in real time, where possible, fromless-hazardous starting materials and then cbemically trans-formed immediately into the rial product. As a selectedexample for semiconductor technology, recent progress isreviewed for the on-demand production of arsine in turnkeyelectrochemical generators. Innovation ofon-demand chemicalgenerators and alternative processes provide rich areas forenvironmentally responsive chemical engineering processingresearch and development for next-generation technology.

The chemical industry, often maligned and undervalued bysociety, has an exemplary past with a key role in elevating thestandard of living of developed countries. Currently, U.S.industry sustains a healthy economic position as one of thevery productive high technologies (1). Its future status,although gauged to be continuously prosperous, will beimperiled by difficult technical and demanding economicchallenges generated by increasing pressures to transformexisting industrial chemical processes into environmentallyneutral manufacturing operations (2). Fortunately, U.S. in-dustry possesses great capacity for technical innovation andreinvestments for the future, which are sustained by itseconomic health.

Economically, the industry is unequivocally successfuland through the manufacture of chemical feedstocks, deriv-atives, and production of materials, has maintained a positivebalance of trade consistently over several decades. Thus, the

Table 1. High-technology industries based on chemistryChemicals Materials

Agrochemicals CeramicsElectronic reagents GlassPaints and solvents Metals and alloysPetrochemical feedstocks PaperPharmaceuticals Plastics and rubbersSoaps and detergents Synthetic fabrics

U.S. is afforded one of its few remaining globally competitiveedge high-technology industries (1). In addition to its positiveimpact on the economy, the industry is crucial in the main-tenance of the high standard of living that is now common-place in developed countries. Chemistry plays a key role infood production, in the supply of materials for clothing andshelter, in preventing disease, and in providing health careproducts. Chemical technology also is the cornerstone onwhich a number of other materials industries depend, asindicated in Table 1.

Despite the pivotal role of chemistry in advancing tech-nology, the benefits derived are frequently erroneously per-ceived to be counterbalanced by a Gaussian distribution ofdestructive manifestations. Predictably, misuse, abuse, andaccidents involving chemicals and hazardous materials canproduce catastrophic consequences for humans and for theenvironment (2, 3). However, in a manner somewhat analo-gous to the usage of medicine, appropriate chemicals whenused properly in correct amounts more often produce thedesired beneficial results. This dichotomy of beneficial anddestructive impacts of chemicals is exemplified well bypesticides and herbicides, by explosives and fuels. Manycommodity chemicals used for these purposes are intrinsi-cally dangerous to humans and animals. Still other chemicalreagents with unique properties can be designed specificallyfor their lethal properties and exploited because of persistentstability. Involvement of such hazardous chemicals in envi-ronmental incidents and accidents contributes to the spreadof chemophobia among the general public. Certainly, mediacoverage of events such as those listed in Table 2 is news-worthy. Unfortunately, the extensive and disproportionatecoverage sometimes given to such incidents, but not reportedfor chemical benefits, perpetuates a negative perception ofchemistry that has become the more frequently held imageamong the average citizen. Apparently, sensational coverageof several maladies can easily overshadow the entire historyof tremendous benefits that far exceed the detriments of theindustry.

Abbreviations: EPA, Environmental Protection Agency; HPTC,high-priority toxic chemical; CFC, chlorofluorocarbon; PCB, poly-chlorinated biphenyl; CVD, chemical vapor deposition; MES-FET,metal semiconductor-field effect; VPE, vapor phase epitaxy; MBE,molecular beam epitaxy.

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Safeguards against the potential dangers associated withthe production and use of chemicals are necessary. Manychemicals are highly toxic and accumulate in biologicalsystems, in waterways, in soil, and in the atmosphere.Consequently, federal and state agencies implement andenforce compliance regulations to provide environmentalprotection. Historically, the chemical industry has been wellpoliced and monitored. Legislative mandates continue to beissued to protect industrial workers, the general population,and the planet from the long-term effects of chemical expo-sure. Under the control of the Occupational Safety andHealth Administration (OSHA), and with the surveillance ofthe Environmental Protection Agency (EPA), industry ingeneral and the chemical industry specifically have embodiedsafety as one of the premium parameters of manufacturing.This emphasis on and cognizance of the need for protectionof people within the work place from chemical exposure andother hazards are now being paralleled by an increasingawareness of the vital need to protect the planet fromlong-term environmental degradation resulting from man-made chemicals (2). To achieve this end, more stringent U.S.legislation has been passed recently and international coali-tions are forming to retard global environmental pollution.A great impetus for the "greening of the planet" (environ-

mentally consciousness industrialization) is provided by newmandates to control air pollutants. The Clean Air Act amend-ments of 1990 target 191 air toxic chemicals for reducedemissions. Several of these chemicals have been designatedas high-priority toxic chemicals (HPTCs) (Table 3). This labelimplies that there is a sufficient data base of experimental andtoxicological information to indict these chemicals as pre-senting significant risks to human health and the environ-ment. Among these compounds are included 1,2-dichloro-ethylene, other chlorocarbons listed in Table 3, and chloro-fluorocarbons (CFCs) that catalyze the destruction ofatmospheric ozone. These chemicals are sufficiently destruc-tive to the environment that their large-scale usage is sched-uled to be either drastically reduced or phased out over thenext decade (1). The Montreal Protocols specifically stipulatean international agreement to terminate the commercial pro-duction of ozone-depleting CFCs by 2000 (4).More stringent controls of water pollutant chemicals are on

the horizon as well. The passage of the Safe Drinking WaterAct, which takes effect in 1992, doubles the number ofpollutants subject to federally enforceable drinking waterstandards. The regulation sets maximum contaminant levelsfor four widely used pesticides (alachlor, aldicarb, atrazine,and pentachlorophenol); 13 other pesticides; 10 volatile or-ganic chemicals; polychlorinated biphenyls (PCBs); and 8inorganic chemicals including cadmium, nitrate, and nitrite.Ultimately, -85 contaminants will be regulated by enforce-able standards by July 1992 (5).Other legislation is aimed at cleaning up extensively pol-

luted land and waterways and regulating hazardous materialsand wastes. The Superfund Amendments and Reauthoriza-tion Act (SARA) regulates the tracking of extremely hazard-ous chemicals and in tandem with the Toxic SubstancesControl Act provides the EPA and states with the authorityto control the industrial use of hazardous materials (6). The

Table 2. Chemicals and sites involved in incidents or accidents

Chemicals Site(s)

Agent Orange Bhopal, IndiaLead pigmented paint Love Canal, NYDDT Persian GulfDES Superfund sitesPCBs Valdez, PrinceThalidomide William Sound

DDT, dichlorodiphenyltrichloroethane; DES, diethylstilbestrol.

Table 3. HPTCs

Benzene Mercury (cpds)Cadmium (cpds) Methyl ethyl ketoneCarbon tetrachloride Methyl isobutyl ketoneChloroform Nickel (cpds)Chromium (cpds) 1,1,1-TrichloroethaneCyanide (cpds) TrichloroethyleneDichloromethane XylenesLead (cpds) Dioxins

Evaluated by the EPA as presenting significant risk to humanhealth and the environment. cpds, Compounds.Resource Conservation and Recovery Act (RCRA) and re-cent state supreme court interpretations are establishing atrend that tends to hold previous commercial landownersforever liable for the cleanup and for damages resulting frompollution generated by industrial and technological activity.Cradle-to-grave accountability for the generation, treatment,and disposal of hazardous materials appears to be the rule forthe 1990s and beyond.

Technology for Preventing Pollution

Scrutiny of the total environmental picture involves an anal-ysis of the primary components compliance, recycling, wastetreatment, and site remediation. Requirements for compli-ance are becoming more stringent at the same time that costsfor remediation and treatment are skyrocketing. These trendscompel industries to examine and also exploit the economyof recycling-based processing. Clearly, approaches to pollu-tion prevention must be incorporated into chemical process-ing and manufacture. In view of rapidly expanding ecologicalconsciousness, and the compelling economics of environ-mental compliance, innovation of pollution-preventing tech-nology as opposed to add-on waste treatment and remedia-tion technology is the preferred approach for next-generationmanufacture of chemicals.

Already the U.S. is a world leader in the development ofenvironmental technologies and in the practice of environ-mental protection (7). This state of readiness results fromenlightened management and the influences of federal com-pliances, which have induced the chemical industry to take aleadership role in implementing safety awareness. A similartrack record might well be expected for the industry's lead-ership in institutionalizing environmentally responsive pro-cessing and manufacture. To accomplish this new mission,chemicals and materials manufacturing ofthe future will needto deliberately develop and exploit new pollution preventiontechnology and strategies. Within this regime of operation,the industry may be compelled to innovate environmentallyresponsive processes and procedures to replace existing onesthat have required decades to develop. By contrast, envi-ronmentally suitable alternatives will need to be innovatedwithin a few years. In the achievement of these endeavors,

Table 4. Chemicals in 1990 top 50 largest volume productsRank Substance lb x 10-915 Ethylene dichloride16 Benzene17 Xylenes18 Vinyl chloride19 Ethylbenzene20 Styrene23 Formaldehyde25 Toluene27 Ethylene oxide29 Ethylene glycol39 Acrylonitrile

13.3011.8610.9010.658.998.026.416.105.585.033.30

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Table 5. Properties of N-methyl-2-pyrrolidone substitute formethylene chloride

Methylene N-Methyl-Property chloride 2-pyrrolidone

Solvent power Excellent ExcellentFlammability None Flash point 910C

(auto. ign.) 2700CSolubility in H20 2% (vol/vol) Completelybp 39.70C 2020Cfp -950C -250CToxicity Narcotic* Eye, skin* irritantBiodegradable Moderate RapidState Liquid Liquid*Total human toxicity still not unequivocally defined.

one expects that chemical substitutes and on-demand pro-cesses will receive focused attention as alternatives to exist-ing technology that pose environmental problems.

Chemical Substitutes and Replacements

The most viable environmentally responsive strategy forHPTCs includes reduced usage, phased-in replacement, andultimately, where fully warranted, phased-out large-scaleproduction. Thus, the production ofenvironmentally suitablesubstitutes for HPTCs is an immediate challenge for thechemicals industry. Among the targeted group of chemicalsidentified in Table 3, several are commodity products man-ufactured in high volume. As shown in Table 4, methylenechloride, benzene, and the xylenes rank among the top 20chemicals produced in 1990 (8). To preclude economic lossesassociated with commodity chemicals being phased out, theindustry is introducing replacements at an astounding pace.Already the substitute, N-methyl-2-pyrrolidone, is beingcommercialized as a promising replacement for methylenechloride. The properties of this environmentally compatiblechemical replacement are compared in Table 5 with proper-ties that dictate the industrial applications of methylene

chloride. Whenever possible, substitutions of an environ-mentally compatible reagent for one that becomes targetedfor phased-out manufacture is a viable alternative that iseasily exploited when no or minimal capital investment isinvolved. Process changes that eliminate the use of thetargeted chemical are even more valuable.

Simple substitutes cannot replace many commodity chem-icals that are unique precursors for the synthesis of second-ary derivatives and materials. For example, formaldehydeand vinyl chloride both have unique properties and tremen-dous industrial value, while also being hazardous to humans.Where such chemicals do not bioaccumulate, have wellknown harmful threshold levels for humans, and are con-trolled by exceedingly stringent regulations that safeguardtheir storage, transport, handling, and work-place exposure,labeling as HPTCs is inappropriate. It is imperative, how-ever, that next-generation methodologies be innovated tofurther ensure the protection of society and the environmentfrom "known-to-be-harmful" chemicals.

On-Demand Chemical Generation

In conventional large-scale production of hazardous chemi-cals, several phases pose environmental risks. As depictedschematically in Fig. 1, large-scale chemical processingplants are engineered to achieve synthesis, separation, andtemporary on-site storage ofvarious products. Subsequently,precursor chemicals are transported by appropriate vesselsthrough the public domain to customer premise sites, wheresecondary storage provides a stockpile of chemicals forcustomer use. For dangerously toxic chemicals, the twostages of storage and the possibility of accidents duringtransport pose acceptable risks that are now dealt withrelatively easily on a daily basis.An alternative to conventional processing of extremely

toxic chemicals is on-demand generation, which is diagramedin Fig. 2. Conceptually, this approach involves the dynamicreaction of less-hazardous precursors to generate the more-hazardous product only when it is needed. In an appropriate

CHEMICAL PLANT-_ -_-_ _ _

I

I.IRAI**

I II

I."I I _v

CUSTOMERPREMISE

I

m - m - - - - - - - ---- ---- - m -mm m i

FIG. 1. Conventional production of commodity chemicals.

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ENVIRONMENTALLYSAFE

PRODUCTION

FIG. 2. Schematic of on-demand generation of commodity chemicals.

reactor (R1), the precursors are dynamically reacted to gen-erate a product stream of the desired toxic chemical, whichis in turn fed in real time into a chemical process reactor. Thison-demand generation ofthe toxic chemical at the customer'ssite and its subsequent real-time consumption in manufactureeliminates storage and transport of dangerously toxic chem-icals. Innovation of on-demand generators for extremelyhazardous chemicals is the alternative that might well be theapproach of the future for chemical products such as vinylchloride, formaldehyde, methylisocyanate, phosgene, hydra-zine, ethylene chlorohydrin, and other chemicals. The de-velopment of large-scale, economic, on-demand generatorsinterfaced to processes for the real-time consumption oflethally toxic chemicals in manufacturing could be an ex-tremely fruitful venture for the chemical process industry ofthe 21st century.

Alternative Electronic Chemicals

Alternative precursor reagents for use in semiconductormanufacture are needed to further improve margins of safety.All of the reagents arsine, silane, dichlorosilane, germane,phosphine, and aluminum and indium alkyls are essentialprecursors for fabricating electronic devices. These chemi-cals, some lethally toxic gases and others pyrophoric, havebeen supplied in compressed gas cylinders and used safely indevice manufacture for >3 decades. However, there is theever-present potential hazard associated with the use ofcompressed cylinders. This ultimate concern for safety is the"sudden release hazard" associated with a catastrophicfailure of the compressed gas cylinder or its associated valve.

Table 6. Toxicity data for substituted arsine

LC50,Name Formula ppm* Rating

Arsine H3As 42 Highly toxicDimethylarsine HAs(CH3)2 164 Moderately toxicTrimethylarsine As(CH3)3 >14,027 Practically nontoxict-Butylarsine H2As(Bu-t) 90 Highly toxic

*Lethal concentration in ppm where 50% of test animals expiredduring a 4-hr exposure period.

Where large amounts of arsine are required for manufacture,planning for this unlikely event includes storage of arsine inremote outdoor or rooftop facilities. These facilities canrequire expenditures of up to $1 million to accommodatecontainment and storage and to provide transport lines to thepoint of use in the laboratory. Despite these expenses, theU.S. electronics industry has developed optimized proce-dures for handling toxic gases and has installed state-of-the-art facilities for containment, storage, recovery, and disposalof toxic reagents.Due to the acute toxicity of arsine (more toxic than

hydrogen cyanide), investigations have been conducted toexamine alternatives to arsine in cylinders. A possible solu-tion to the hazard associated with the sudden release ofarsinestored in compressed cylinders is containment of the gas atatmospheric pressure. Investigators at the Naval ResearchLaboratory have demonstrated atmospheric-pressure stor-age ofAsH3 in zeolites at 23°C (9). Desorption ofthe adsorbedreagent (-25% by weight) below 190°C was demonstratedalong with the growth of GaAs and AlGaAs materials byvapor-phase epitaxy. This approach eliminates the hazardassociated with compressed gas cylinders. However, it doesnot circumvent the limitations imposed by safety guidelinesthat restrict storage of arsine to 100 g or less. While therestriction of the storage of the toxic gas to 100 g at atmo-spheric pressure enhances safety in the work place, devicemanufacture can be affected negatively. Device yields andreliability are susceptible to fluctuations of reagent qualityassociated with frequent changes oflow-capacity systems. Infact, frequent changes of the arsine source may actuallydecrease safety by increasing the opportunity for humanerror.We have devised other alternatives to arsine in compressed

gas cylinders. In principle, the preferred solution is thereplacement ofarsine by completely nontoxic reagents. Prog-ress in developing nontoxic, volatile alternatives to arsine hasoccurred. As shown in Table 6, lethally toxic arsine is madeincreasingly less toxic by alkylation. The fully substitutedreagent As(CH3)3 is practically nontoxic according to con-temporary chemical standards. In addition, as the substitu-tion increases, the reagent becomes less volatile. As(CH3)3 isa liquid at room temperature. This fully alkylated methyl

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FEEDBACK LOOP

ON - LINIE PROCES SCONTROL MIONITOR

PRODUCT STREAM

FIG. 3. Components of on-dem=

analog of arsine, trimethylarsine, has been investigated indetail (10, 11). Although this reagent is useful in pyrolyticchemical vapor deposition (CVD) deposition ofGaAs at 4000Cor more, the resulting film contains considerable levels ofcarbon incorporation (>1016 atoms per cm3). Co-deposition of

land electrochemical arsine generator.

C into the GaAs layer is minimized by using the partiallyalkylated reagent, tertiarybutylarsine, [H2A,(Bu-t)] (12).Since this material is only somewhat less toxic than arsine, itstill requires precautions in use. Because it is a volatile liquidand not a gas at room temperature, (t-Bu)AsH2 can be handled

FIG. 4. On-demand electrochemical arsine generator.

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Table 7. Purity of electrochemically generated arsine

Arsine 83.49%Hydrogen 16.50%Nitrogen 33 ppm

Other impurities not detectable by highest sensitivity mass spec-trometry: H2AsOH, H2AsCH3, BiH3, CO, C02, Ga2H6, GeH4, H2Se,H20, H2Te, 02, PbH4, PH3, SbH3, SiH4, SnH4.

more safely than cylinders of compressed arsine gas. Acommercial source ofa high-purity product has been identifiedand used by device engineers to fabricate metal semiconduc-tor-field effect transistor (MES-FET) devices that meet cur-rent-voltage and other performance specifications (13).To eliminate arsine storage, a technique to generate it

on-demand in desired quantities and deliver it in real time tothe reactor has been devised (12). The technique is based onelectrochemical on-demand synthesis of the reagent at anarsenic metal cathode in a suitable electrolytic cell containing1.0 M potassium hydroxide. Fig. 3 is a schematic of theprototype pilot-scale unit. This unit has a total generatingcapacity of 10 lb of arsine delivered over a wide range ofconcentrations (2-85% in H2), at selectable pressures up to 60psig, and at variable flow rates up to 1.0 liter/min. Thesereagent fluxes meet all requirements for CVD, vapor phaseepitaxy (VPE), and molecular beam epitaxy (MBE) andsatisfy most conditions for (MOCVD).A photograph of the first commercial on-demand generator

of a precursor for semiconductor device fabrication is shownin Fig. 4. Within the electrochemical cell, a unique packed-bed cathode compartment permits up to 10 lb of pure arsenicto be reduced to arsine. The electrode compartment isdesigned for uniform current distribution, thus ensuringcontrolled consumption of the cathode material while mini-mizing the simultaneous formation of hydrogen. In thismanner, arsine yields of nearly 85% are obtained in H2 by thereactions

As(s) + 3H20 + 3e -* AsH3(,) + 30H-

2H20 + 2e- H2g) + 20H-Other components of the generator include two drying col-umns in tandem and automated pressure and flow regulationcontrols. The entire system is controlled by a microprocessorand a direct-current power supply. This system is designed tobe housed completely within a standard toxic-gas cabinet.AT&T has licensed Electron Transfer Technologies (Princ-eton, NJ) to supply the system commercially.The high quality of generated arsine is established by

detailed chemical characterizations. Arsine and hydrogenlevels measured by on-line acoustic time-of-flight techniquesare given in Table 7. The absence of impurities of concern todevice growers is assured by on-line mass spectrometry.Moisture is also measured specifically by a high-sensitivitysensor. The moisture level, 80 + 2 ppb, is more than an orderof magnitude lower than the best purity quoted by commer-cial suppliers of arsine in cylinders. Oxygen impurities havenot been detected by any of the applicable analytical meth-ods. During periods when the generator is in idle mode,

nitrogen may slowly effuse from the pores of the zeolites usedin the drying column. Occasionally, up to 33 ppm of nitrogenhas been measured. Fortunately, this inert impurity is innoc-uous for all CVD applications of arsine.

After verification of the purity of the arsine product, thegenerator was interfaced to a hydride VPE reactor. InGaAs/InP MES-FET devices have been fabricated and shown toequal or exceed the best performance of identical devicesfabricated with arsine from commercially available cylinders(14). Recently, the generator has been interfaced to andproven compatible for MBE fabrication of materials. GaAsand InGaAs materials were fabricated in tandem using on-demand generated and cylinder arsine. GaAs from the gen-erated arsine were 103 lower in impurities and InGaAs werea factor of 4 lower in impurities than corresponding materialsproduced from an arsine cylinder. Both laser-induced pho-toluminescence and current-voltage characterizations con-firmed the superior purity of the materials fabricated withon-demand generated arsine.

Future Directions

The development of nontoxic, and environmentally compat-ible alternatives for critically important precursor reagentsfor semiconductor device manufacture is greatly importantand worthy of comprehensive investigations. In those caseswhere nontoxic alternatives for Si, As, P, In, Al, and Gareagents cannot be produced, the next best alternative ofproducing existing toxic precursors by on-demand turnkeygenerators must be pursued vigorously. In addition, chemicalengineering research to develop clever methods for largescale on-demand production of hazardous chemicals forimmediate conversion into benign products will provideopportunities for chemical engineers to develop environmen-tally responsive technology to revolutionize chemical pro-cesses for the next century.

1. Landau, R. & Rosenberg, N. (1990) Invent. Technol., 58-63.2. Heafon, G., Repetto, R. & Sobin, R. (1991) Transforming

Technology: An Agenda for Environmentally SustainableGrowth in the 21st Century (World Resource Institute, Wash-ington), p. 5.

3. Medvedev, G. (1991) The Truth About Chernobyl (Basic Books,New York).

4. Dombrowski, S. L. S. (April 1991) Environ. Protect. 2, 14-22.5. News Updates (1991) Environ. Protect. 2, 8.6. McGregor, G. (1991) Environ. Protect. 2, 25, 54.7. Lepkowski, W. (1991) Chem. Eng. News 69, 13-16.8. Relsch, M. S. (1991) Chem. Eng. News 69, 13-16.9. Sillmon, R. S. & Freitas, J. (1990) Appl. Phys. Lett. 56,

174-176.10. Lum, R. M., Klingert, J. K. & Kisker, D. W. (1989) J. Appl.

Phys. 66, 652-655.11. Lee, P. W., Omstead, T. R., McKenna, D. R. & Jensen, K. F.

(1988) J. Cryst. Growth 93, 134-142.12. Valdes, J. L., Cadet, G. & Mitchell, J. W. (1991) J. Electro-

chem. Soc., in press.13. Lum, R. M., Klingert, J. K., Ren, F. & Shah, N. J. (1990)

Appl. Phys. Lett. 56, 379-381.14. Buckley D. N., Seabury, C. W., Valtes, J. L., Cadet, G.,

Mitchell, J. W., DiGiuseppe, M. A., Smith, R. C., FilipesJ. R. C., Bylsma, R. B., Chakrabarti, U. K. & Wang, K.-W.(1990) Appl. Phys. Lett. 57, 177-182.

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