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The GMA 2010 Logistics Benchmark Report
Performance reaches all-time high during economic depression
Grocery Manufacturers Association The Grocery Manufacturers Association (GMA) represents the world's leading food, beverage and consumer products companies. The Association promotes sound public policy, champions initiatives that increase productivity and growth and helps ensure the safety and security of consumer packaged goods through scientific excellence. The GMA board of directors is comprised of chief executive officers from the Association's member companies. The US$2.1 trillion food, beverage and consumer packaged goods industry employs 14 million workers, and contributes over US$1 trillion in added value to the nation's economy. For more information, visit the GMA Web site at www.gmaonline.com.
IBM Global Business Services With consultants and professional staff in more than 170 countries globally, IBM Global Business Services is the world's largest consulting services organiza- tion. IBM Global Business Services provides clients with business-process and industry expertise, a deep understanding of technology solutions that address specific industry issues, and the ability to design, build and run those solutions in a way that delivers bottom-line business value.
The Grocery Manufacturers Association and IBM are pleased to bring you the 2010 Logistics Benchmark Report.
The consumer packaged goods (CPG) industry's challenges in 2009 and 2010 have prompted GMA and IBM to issue the most wide-ranging and comprehensive logistics survey report in the history of this semi-annual research initiative commissioned by the GMA Logistics Committee and conducted by IBM. Inside you'll find the latest practices, trends and operational benchmarks in key areas of CPG manufacturers' supply chain operations. As we have done in previous years, we have included analyses of more than 50 questions answered by supply chain leaders at 26 top-tier CPG manufacturing companies. We have also incorporated a review of specific causes and trends that affect those responses.
The GMA 2010 Logistics Benchmark Report was conducted by IBM as commissioned by the GMA Logistics Committee. It focuses on issues pertaining to operational planning, inventory management, outsourcing strategies, distribution, information technology and strategic supply chain practices. As you'll read, supply chain initiatives are working, and supply chains have become more efficient since our last survey report was published in 2008. You will also see that there is no one-size-fits-all solution to challenges. Each logistics operation has its own set of opportunities and challenges – compelling supply chain leaders to pursue new practices across the board.
There is certainly much happening in terms of successful supply chain practices in the CPG industry, and we hope you will find this report informative and insightful. GMA and IBM look forward to discussing these findings, issues and analyses.
Karen Butner Supply Chain Management Global Leader IBM Institute for Business Value
Jeanne Iglesias Senior Director, Supply Chain and Technology Grocery Manufacturers Association
Executive Summary
Supply Chain Performance Improved In All Categories: Cost, Service and Time
Logistics Costs Are Down – But Freight Costs Remain High
Customer Service Is Improving. So Why Aren't Customers Satisfied?
Inventory and Demand Management Practices Are Working – and Well
Key Performance Indicators Reach an All-Time High – But What Will the Decade Bring?
The GMA 2010 Logistics Benchmark Report examines and highlights emerging practices, trends and operational benchmarks in crucial areas of CPG manufacturers' supply chain operations. IBM Global Business Services conducted the survey in conjunction with the Grocery Manufacturers Association beginning in December 2009 through January 2010. The survey included more than 50 questions to supply chain leaders of top-tier CPG brands – focusing on issues such as strategic supply chain objectives, distribution and transportation practices, outsourcing strategies, alliances, information technology, demand planning and inventory management.
Profile of respondents
The GMA 2010 Logistics Benchmark Report was completed by logistics executives at 26 GMA member companies. The survey included 21 respondents who also participated in the 2008 survey, as well as five new participants. Companies responding to the 2010 survey ranged from those with annual revenue of less than US$500 million to more than US$14 billion in annual revenue. The largest number of respondents represented businesses in the US$1 billion to US$10 billion range. The average annual revenue among all respondents was US$5.8 billion. Most of the respondents represented the following product categories: dry (83 percent), refrigerated (33 percent) and frozen (29 percent). Others categories represented included food service, HBC and cosmetics, and dairy. The majority of the revenue represented (57 percent) was comprised of dry grocery.
We wish to thank the members of the GMA Logistics Committee who were involved in the survey design and review of the results. We especially want to thank all of our respondents who completed the 2010 GMA Logistics survey, as well as our 2008 participants. The combined results are used for comparative trend analysis.
The word "volatile" has been widely used by both the financial and mainstream media to describe our global marketplace. In such an environment, companies must dig deep across their supply chains to optimize operations, heighten efficiencies and combat the impact of a challenging economy.
Due in large part to downward sloping production, disposable income, employment and consumer expenditures, worldwide gross domestic product (GDP) growth was down 0.8 percent in 2009. 1 Yet in the midst of this global recession, when volatility and customer demand variability are challenging all companies and all industries around the world, the CPG manufacturers and distributors we surveyed report all-time high performance. Congratulations!
The GMA 2010 Logistics Benchmark Report confirms that a vigilant focus on customers and a keen eye on the bottom line can ultimately drive business performance.
For many companies, the past two years have been all about cost containment and reduction. CPG manufacturers and distributors managed to improve logistics costs in many categories while simultaneously improving customer service levels. What's more, they also improved days of inventory, the associated working capital expense and collection cycle times.
Logistics costs are down, but freight costs remain high
Logistics costs as a percentage of sales were down from the past four years – hovering at 6.9 percent. At first glance, we might attribute this statistic solely to increases in manufactured product prices. While it is true that prices rose in many categories, costs were lower when measured by cost-per-case and hundredweight. But the big surprise, given the overall decrease in logistics costs, was that freight costs continue to climb – up 11 percent from 2008. Distribution and transportation practices reveal continued high effectiveness ratios in outsourcing, intermodal transportation and IT investments in Warehouse Management Systems (WMS), Transportation Management Systems (TMS) and other technologies.
Customer service is improving. So why aren't customers satisfied?
On-time delivery performance has reached paramount levels and exceeded targets. Case fill rates are up. Perfect order levels are higher. Yet customer satisfaction ratios have decreased from 2008. Are customers' requirements more difficult to satisfy in these trying times, or are manufacturers' scorecards in need of adjustment? Top- performing manufacturers have a different story to tell.
Inventory and demand management practices are working – and well
Agile inventory-management controls and attention to demand variability were at an all-time high during this economic recession period. Days of supply are at 36.4 on average, down from 45. Turns have improved. Sales and operations planning (S&OP) processes and integration are credited for improving forecast accuracy. While make-to- stock strategies dominate this industry sector, continuous replenishment and vendor- managed inventory programs linked to point-of-sale are growing initiatives.
Key performance indicators reach an all-time high – but what will the decade bring?
Optimizing supply chain performance, productivity and responsiveness are increasingly important to achieving cost-containment and service-level objectives. As we begin a new decade, where should supply chain leaders direct their attention? This study revealed four key focus areas:
• A demand-driven supply network: Accurately predict demand and be in a position to react to demand variability through dynamic sourcing and allocation of all needed resources. The integration of customers' wants and needs must permeate the supply chain – from inception to delivery – with the entire global network focused on the end shopper/consumer.
• Enhanced visibility: Move beyond realtime communication to open collaboration – allowing people across the supply network to connect and communicate faster, share decision making and work transparently in a virtual, secure, globally integrated environment that enhances visibility to events, suppliers, service providers, customers and other key connections.
• Sustainability: The best results in terms of cost and efficiency can be achieved by balancing the mix of cost and service globally, while sustaining the health of the company and the planet.
• Risk management: Risk management policies and programs are inclusive, and should be adjusted in situations where there is a probability of an event occurring. Mitigation strategies should be in place and known by all to help ensure immediate response.
As companies develop their supply chain transformation agendas for the next decade, the findings of this study should provide new insights, confirmation of widely-held beliefs, and a valuable industry baseline against which companies can measure their performance going forward.
Consumer-product supply chain operations continually feel the pressure to manage the cost equation – all while meeting the strategic objectives of providing superior customer service and driving growth within the business. At a time of global recession, the pressures are even greater. Consider the modern enterprise's entire value proposition and value chain. Leadership must balance a precarious profitability equation – hoping that product development, marketing and distribution partners can continue to drive revenue through volume, pricing or both while leaning heavily on areas like logistics and procurement to control cost. This presents supply chain executives with fewer levers to pull as they continue to battle commodity prices and other rising expenses such as freight costs – expenditures that are beyond their control. There is a constant "juggling" act that must take place in balancing rising expenses and constantly increasing customer expectations.
Reduced logistics costs, increased customer responsiveness and profitable growth still rank as the top three objectives for supply chain executives, just as they did in 2005 and 2008. However, as Figure 1 shows, in the midst of a global economic downturn, much more emphasis is being placed on taking inventory out of the pipeline to improve working capital efficiencies. The respondents in our study were also positive about the impact of their various supply chain initiatives in the past two years: to decrease costs (62 percent), improve efficiency (58 percent) and raise customer service levels (44 percent).
Reduced logistics cost
Increased customer responsiveness
Profitable growth
Working capital efficiency
Improved quality
Reduced order to delivery cycle time
Percentage of respondents
Source: IBM Institute for Business Value, 2010 GMA Logistics Survey.
Logistics cost as a percentage of sales has decreased
The supply chain executives we surveyed have hit a grand slam. These manufacturers and distributors report having improved:
• Logistics costs
• Service levels for on-time delivery and case fill rates
• Order size and shipment size
• Outsourcing ratios and effectiveness
• Inventory days of supply and turns
• Forecast errors
• Cash-to-cash cycle time and days sales outstanding
Since 2008, logistics costs as a percentage of sales have decreased significantly – to 6.75 percent. In 2005 and 2008, they hovered at a flat 6.9 percent of sales. One's first reaction might be that surely, manufactured product price increases have served to mask the impact of rising logistics costs. To some degree this is true, as indicated by the overall order dollar value increasing (see Figure 2). Not only have revenues risen from price hikes; both average order size and average shipment sizes have increased by a consistent 4 percent, which would also indicate that consolidated order-shipment practices (versus smaller shipments more frequently) have remained intact during this period.
Logistics cost as a percent of sales
Order dollar value
66% Increasing 24% Staying the same 10% Decreasing
Cost per case and cost per cwt have decreased to levels that more closely resemble 2005
At the same time, there have also been remarkable improvements in cost management. Case cost has decreased to levels comparable to 2005, and the same is true for cost per hundredweight. This applies in all categories: outbound customer transportation, intra-company transportation and distribution center activities. Cost per case averaged 47 cents in 2005, 69 cents in 2008, and was down to 44 cents in 2010. Costs per hundredweight were US$2.52, US$7.40 and US$3.98 respectively. The only product cost category that was higher than in 2008 was custom packaging – a result of key customers' increasing requirements for specialized packaging.
Cost per case by function (US$)
Cost per cwt by function (US$)
Transportation costs account for the largest percentage of total logistics costs, the allocation of which has not changed significantly from 2008. Outbound customer transportation and intra-company transportation remain the largest categories, with only a 1 percent change from 2008, which was 64 percent combined. Distribution costs are the next highest category. (See Figure 4).
Logistics cost by function
Freight costs continue to climb – up 11 percent from 2008, while fuel prices dropped during the same time
1% Other
29% Distribution centers 39% Outbound customer transportation 24% Intra-company transportation
Management activities/overhead
But when we dig a bit deeper into the transportation cost equation, we find that despite the great news of decreased total logistics costs as a percentage of sales and case cost reductions, freight costs continue to climb – up 11 percent from 2008, at US$2.05 cost per mile against a goal of US$1.83. This occurred at a time when diesel fuel prices plummeted and remained relatively low at 2005 levels. (See Figure 5).
To what can we attribute this rise in freight costs? According to the American Trucking Association, there has been a shortage of qualified truck drivers, which has resulted in increasing wage rates. In 2008, more than 2,300 trucking companies went bankrupt, including some sizable businesses. There was a period when resources were scarce versus demand. Other factors prevail here as well. Trucking companies are under pressure (their form of higher customer demands) to provide more value-added services, such as integrated scheduling, track and trace, and GPS capabilities. Also, insurance rates have increased. All of these factors are being passed on to the manufacturer/distributor and likely to the end consumer. 2
Freight cost per mile (US$)
Diesel fuel cost over time (US$)
Source: IBM Institute for Business Value, 2010 GMA Logistics Survey; U.S. Energy Information Administration.
Among the transportation strategies that companies are using to better control costs while maintaining service levels is to ship directly to the customer from the plant or plant warehouse, as opposed to using intermediate storage and incurring additional handling time and costs at the distribution center. Others are increasing trailer utilization and the use of drop trailers. Customer pick-up is also increasing. Premium freight charges are down. On average, empty truck mileage percentages are lower. Some of these improvements are due to management practices, but a lot of the credit may be attributable to improvements in information technology (IT). The predominance of IT spending has been in transportation management systems and warehouse management systems, exceeded only by IT expenditures in electronic data interchange. Vendor-management inventory programs and advanced ship notification are other areas that are proving to be highly effective in terms of value received for the IT dollars spent.
Outsourcing of transportation and warehousing/distribution centers is showing very high growth – with over 50 percent of companies extensively outsourcing transportation. Other growth areas for outsourcing are facilities maintenance and customs/export management. IT outsourcing for logistics processes is slightly on the rise, but what is interesting here is the increase in effectiveness – up from 86 percent in 2008 to 100 percent in 2010. Other outsourcing activities received a 100 percent effectiveness ratio except for audit and payment services, which came in at 94 percent. This would lead to the recommendation to continue to explore and expand the role of outsourcing for various functions.
When choosing transportation providers, carrier selection is based primarily upon service level attainment (95 percent), capability (90 percent) and then unit cost (86 percent). With diesel fuel prices on the rise again, manufacturers/distributors may need new tactics to manage overall transportation cost. One approach is mode shift. Over-the-road and truck load usage is decreasing. Pool shipments are a bit higher, but intermodal is leading the pack, continuing to increase year-to-year – up 5 percent from 2008. The rail industry reduced prices for the past three quarters of 2009, which resulted in a 5.8 percent overall price cut in 2009. However, the industry is forecasting that rail prices will trend upwards this year – assuming that consumer spending also increases as the economy recovers.
What does the future hold for companies continuing to juggle service goals and costs? The 2012 goal for truckload freight cost per mile is US$1.79, which may continue to be a bit aggressive considering the US$2.05 average cost per mile this year. But not for the top 20th percentile. Top performers managed freight costs to achieve US$1.53 cost per mile!
There have been significant improvements in on-time delivery rates to exceed 2010 targets
Case fill rates reach historic highs, but order line item fill rates significantly miss 2010 goal levels
There have been significant improvements in on-time delivery rates – actually exceeding 2010 targets. On-time delivery to warehouse schedules have improved more than two percentage points from 2008 – surpassing the goal of 95.2 percent. The top performers (those in the top 20th percentile) achieved 98.6 percent in on-time delivery to scheduled promise time within 30 minutes. Even more impressive: on-time delivery to the customer's requested date and time was up almost 8 percentage points from 2008. (See Figure 6).
Order-to-delivery cycle time has improved consistently year-to-year from 2005. The percentage of respondents in the six- to ten-day range has remained constant at 48 percent; however, 7.3 percent more are delivering in four to five days. Next- day deliveries are up as well.
Case fill rates are also at historic highs. Hovering since 1999 in the low 98 percent range, they are up to 98.7 percent. (See Figure 7).The leaders (the top 20th percentile) did even better at 99.3 percent. With this achievement in case fill rates, the surprising news is the order line item fill rates. With both order values and average order size increasing (from 18,979 lb in 2008 to 19,837 lb in 2010) order line item fill rates have declined by 2.9 percent from the last reporting period! But once again, there is a clear distinction among the leaders, who reported 99.1 percent rates – a 2.6 percent improvement from 2008 averages.
Case fill rate
Order line item fill rate
Perfect order okay, but not to goal. Customer satisfaction is DOWN!
Despite these marked improvements in customer service levels, customers are still not satisfied. Customer satisfaction is primarily derived from on-time delivery of goods, shipped complete and damage-free. It is also measured through statistics and surveys. According to customer satisfaction statistics, satisfaction is down over 13 percent – from 92 percent in 2008 to 88.7 percent today. Do we differentiate services by customer segments? Not really. Most companies do not treat various customers or segments differently when it comes to providing logistics services. When they do differentiate, it is predominately based upon sales volume and growth potential. There is little to no differentiation based upon account profitability.
Ironically, customer alliances are primarily driven towards the goal of improving customer satisfaction, in addition to reducing overall supply chain cost and improving responsiveness – the same objectives that have resonated throughout this year's data. Goals continue to be set higher for 2012 for most of the major customer service metrics. One important additional measurement is perfect order, which is defined as the percentage of customer orders that are "perfect." For this study, perfect order is the success of the supply chain in delivering the correct product, to the correct location, at the correct time, in the correct package, in the correct quantity, with the correct documentation, to the correct customer (of course) with a correct invoice. It's hard to be perfect. Perfect order rates came in at 79.8 percent against a goal of 83.4 percent – actually up seven points from 2008. Again, the leaders have attained even greater achievement at 89.5 percent.
Stellar improvements have been made in inventory days of supply but aggressive goals remain
So, with perfect order, on-time delivery and fill rates climbing, what will it take to make customers satisfied? Customer satisfaction levels have not met expectations recently – averaging 88.7 percent in 2010 as compared to 92 percent in 2008. This was also significantly under the goal of 96.8 percent. From a trending perspective, customer satisfaction hit a low point in 2005 – falling in the low eighties.
However, perhaps all is not in vain. The leaders (those in the upper 20th percentile) are paving the way, with perfect order performance of 89.5 percent and customer satisfaction at 98.6 percent – up from 2008 averages. No doubt their customers are happy.
Stellar improvements have been made in inventory days of supply from 2008. Days of supply are at 36.4 on average, down from 45 days. The historical days of supply reached an all-time low in 1996 at 34.8 days, and maintained over forty days from 1997 until this year (see Figure 9). This year's average attainment of 36.4 is pretty close to the goal of 35.9 and the continued stretch goal of 2012. During this economic downturn, it is obvious that supply chain managers have turned their attention to finished goods inventory in the pipeline – from plant through the distribution center to final delivery. Although we learned earlier that transportation costs were up, prudence has paid off in reducing inventory levels. Another case in point (case fill rates are up too!) is inventory turns. Here again, we see vast improvements from 2008 – coming in on average at 10 turns as opposed to 8.1 turns.
Make-to-stock remains the predominant strategy for inventory management. There is some growth in vendor managed inventory (VMI), and a bit of an increase in continuous replenishment programs that are linked to actual consumption or point-of- sale (POS) data.
Finished goods inventory performance
Days of supply
Inventory turns
Forecast errors have decreased across the board
So what distribution practices are CPG manufacturers using to realize these performance improvements in inventory management?
The most common distribution tactic is the use of pre-assembled, floor-ready displays and custom pallets. The current spend on pallets in general (distribution center to customer) is US$6.7 million – up 52 percent from 2004. Most pallet usage is CHEP pooling, white wood and iGPS pooling in all categories of usage (production, internal shipments, customer shipments). Use of plastic pallets has only slightly increased in the past few years. Another category of predominant IT spend is in pallet guidelines, with a 100 percent effectiveness ratio.
Collaborative planning, forecasting and replenishment programs (CPFR), collaborative carrier management programs and reverse/differentiated logistics services are all high on the list, with excellent effectiveness ratings. Growing from 2008 is the effectiveness ratio of CPFR – up to 100 percent from 81 percent.
Speaking of collaboration, let's take a look at customer collaboration and forecasting performance. Forecast errors have decreased across the board. Mean Absolute Percentage Error (MAPE) has improved from 2008 in all product categories: nationally (25 percent from 31 percent), by shipping location (34 percent from 37 percent) and by product family (29 percent from 33 percent). Historically, monthly 2010 error rates are more closely resembling 1996 and 2005 numbers, which were both 25 percent or lower. To what can we attribute this improvement in forecasting? Clearly, S&OP practices have evolved. There is more involvement of sales and marketing with all of the supply chain process owners, senior management and finance in demand management consensus building. Another interesting trend is the greater reliance on capturing actual sales orders, including point-of-sales, instead of relying on historical sales trends to more accurately forecast customer demand patterns.
Mean Absolute Percentage Error (MAPE)
By shipping location
By product family
Supply chain key performance indicators are tracking well from year-to-year trending and exceed goals!
demand and inventory management trend that we have observed in other industries
the use of advanced planning and scheduling methods and modeling tools to
provide integrated and statistically relevant business intelligence to planning processes. Many focus on applying advanced analytics to S&OP and forecasting processes, as well as modeling and simulation techniques, to optimize inventory throughout the pipeline while better synchronizing supply and demand at the case level.
Integrated and decision support-based planning practices are clearly meeting objectives to support:
• Financial stability (100%)
• Working capital efficiency (94%)
• Capacity utilization (100%)
• Lowering total delivered cost (85%)
• Profitable growth (95%)
Achieving high performance in the midst of unprecedented economic struggles is a compelling enough story. However, there is even more good news to report. Collection cycles have tightened – all better than the goal, and improved from 2008. Days sales inventory (DSI) is down, days sales outstanding (DSO) is down and cash-to-cash cycle time is also down. (See Figure 11). With such enviable performance, the leaders (those in the top 20th percentile) have clearly raised the bar – with all key performance indicators hitting all-time high levels against goals. (See Figure 12).
Supply chain performance benchmarks – The top 20 percent
Performance measure
Top 20 percent
Logistics cost as percent of sales
On-time delivery to schedule
On-time delivery to request
Perfect order percent
Premium freight charges
Inventory days of supply
Monthly forecast: MAPE
Customer satisfaction
Days sales outstanding
Cash to cash cycle time
Continuous improvement is never out of focus with these supply chain leaders. Survey respondents report that initiatives next on the horizon, either planned or currently engaged, include:
• Demand-driven supply networks
• Enhanced visibility
• Sustainability
• Risk management
Demand-Driven Supply Networks: Intricate synchronization of supply and demand requires collaboration across all supply chain functions – necessary to bring innovative products to market while meeting more demanding customer requirements. Being "demand-driven" requires sensing customer demand and responding immediately to deliver the right product to the right customer when they want it. Collaboration among supply chain partners enables manufacturers to produce exactly what the customer desires to buy.
Accurately predict demand and be in a position to react to demand variability through dynamic sourcing and allocation of all resources. The integration of customer wants and needs must permeate the supply chain – from inception to delivery – with the entire global network focused on the end customer/consumer.
Enhanced Visibility: Supply chain visibility remains the number one challenge of supply chain executives worldwide. 3 We found that visibility in and out of the supply chain is really key. This includes visibility to suppliers, transportation and logistics
providers and, of course, customers. However, it also applies to visibility to other parties that are considered outside of the supply chain, such as financial institutions and government agencies for compliance reporting. What we also learned is that there is
a need for more interaction and integration in the supply chain. What is lacking is the
ability to make sense out of the myriad of supply chain data. This is a growing concern as companies penetrate emerging markets and must meet increasing requirements for compliance and traceability reporting.
We're beyond realtime, and now need to build "open collaboration" – with broad visibility to events, suppliers, service providers, customers and others.
Sustainability: The demanding economic environment requires enterprises to drive greater efficiencies, compete more effectively and be proactive when it comes to energy conservation, environmental stewardship and operational sustainability. Empowered consumers – along with employees, stakeholders and business partners – are also demanding more responsible business practices in package and product design. Many companies are developing a "green" strategy to enhance their competitive position, protect and enrich their brand, improve customer communications and create a "greener" customer experience. Government regulations and compliance standards are, of course, driving the green agenda for many. A cost-efficient sustainability strategy balances trade-offs to optimize efficiencies.
The best results in terms of cost and efficiency can be achieved by optimally balancing the mix of cost and service from a global perspective, while sustaining the company AND the planet.
Risk Management: This study shows that risk management to date is compliance- focused – on the Food and Drug Administration (The FDA), the Customs Trade
Partnership Against Terrorism (C-TPAT) and Free and Secure Trade (FAST) initiatives
– with an average spend of US$70,000 annually. This is a very broad topic. Some think
of financial controls as a way to avoid financial risks. Others are concerned about
unforeseen, catastrophic events or even workplace efficiencies that could otherwise lead to workers' compensation are considerations. However, most supply chain managers think of risk as those day-to-day supply chain disruptions that interfere with meeting customer service requirements while managing costs and other key performance criteria.
Our insights show that leading companies develop risk management policies and programs that are inclusive, and adjusted for the probability of an event occurring. Mitigation strategies are in place and known by all – for immediate response. 4
Our "new normal" global economy has certainly put a strain on most industries, as well as companies, in the past two years of downward sloping production and consumption. Many have "tightened the belt" and focused primarily on cost-reduction initiatives. Some have placed their attention on pipeline inventory optimization, distribution network alignment, and better synchronization of supply in light of highly variable demand.
The CPG manufacturers and distributors represented in this year's study have certainly realized the benefits of focused management attention during trying economic times. We saw that supply chain performance improved in all categories of costs, service and time. Key performance indicators, such as cash-to-cash cycle time, days supply of inventory, on-time delivery, case fill rates and days sales outstanding (DSO) all improved tremendously from 2008 performance and achieved 2010 targets.
Logistics costs as a percentage of sales were at all-time lows – indicating that management is fine-tuning the delicate balance between sales and product pricing and logistical activities to get the right products to customers. We also observed that demand management practices are responsive to better integration of systems and processes in sales and operations planning, which was reflected in the improvement in forecast accuracy and inventory positions.
While customer service levels around perfect order and other indicators were up, we found that customer satisfaction recorded lower than in 2008. Some might say that customers are never satisfied. However, the leaders (those in the top 20th percentile) consistently reported high rankings in ALL categories, including customer satisfaction.
As we embark on a new decade, the challenges may change. Managers' attention may need to shift: to sustainability for compliance and customer satisfaction, to risk management in all categories (while continuing to build smarter supply chains with enhanced visibility) and to a demand-driven supply network point-of-view.
This will require continuous supply chain transformation. The findings in this study should provide new insights, confirmation of widely-accepted beliefs, and an industry baseline against which companies can measure the performance of transformative supply chain initiatives going forward.
About the author
Karen Butner is the Supply Chain Management Global Leader with the IBM Institute for Business Value and an associate partner in IBM Global Business Services. She can be reached at firstname.lastname@example.com.
For more information
Jeanne Iglesias Senior Director, Supply Chain & Technology, GMA
The GMA Logistics Committee
David Adoutte
Ferrero USA, Inc.
Director, Supply Chain and Logistics
Denny Armstrong
The J. M. Smucker Company
Vice President, Logistics & Operations Support
Donald Biggs
Welch Foods, Inc.
Director of Customer Logistics
Dale Brockwell
Kraft North America
Senior Director, Industry Relations, Supply Chain
Sally Brooker
General Mills, Inc.
Director, Customer Supply Chain
Randy Brown
Cargill, Incorporated
Vice President, Transportation and Logistics
Joseph Burton
Mars Petcare US, Inc.
Director - Supply Chain
Allison Campbell
Johnson & Johnson SLC
Director, Logistics
Beth Caron
The Procter & Gamble Company
Supply Chain Leader- Grocery Channel
Scott DeCarlo
Dennis Donelon
PepsiCo Chicago
Director, Customer Service
James Duncan
The Sun Products Corporation
Senior Vice President, Supply Chain & Logistics
Lee Falk
Dean Foods Company
Vice President of Distribution & Logistics
Jim Farnan
Director, Distribution and Logistics Strategy
Jennifer Finci
Grocery Manufacturers Association
Coordinator, Supply Chain and Technology
Timothy Fischer
Bumble Bee Foods, LLC
Senior Vice President, Supply Chain
Robert Gordon
S.C. Johnson & Son, Inc.
National Supply Chain Manager
Thomas Gravelle
Hormel Foods Corporation
Director, Logistics, Transportation & Customer Service
Julie Grove
StarKist Company
OSA Consultant
Bruce Hancock
The Hershey Company
Director, Customer Supply Chain Management
Mark Hojnicki
ConAgra Foods
Jeanne Iglesias
Senior Director, Supply Chain and Technology
Mary Long
Campbell Soup Company
Senior Director, Collaborative Supply Chain Solutions
Louis Martire
Energizer Holdings, Inc.
Vice President, Trade Development
John McKillop
Nestle Purina PetCare Company
Director, Product Supply Excellence
Craig McLaughlin
Cadbury Adams USA LLC
Vice President, Logistics & Customer Operations
Leona Meikle
Land O'Lakes, Inc.
Director of Logistics
Jim Mentone
Director Distribution Operations & Strategic Planning
Donna Olszowka
Georgia-Pacific LLC
Vice President of Customer Solutions
John Phillips
PepsiCo, Inc.
Vice President, Customer Supply Chain & Logistics
Laura Poljanac
Senior Director, Supply Chain
Bob Richardson
The Clorox Company
Director of Sales, Customer Development
Jack Ryan
Nestle USA, Inc.
Director of Customer Logistics, Brands and Prepared Foods
Todd Schultz
Bush Brothers & Company
Stephen Sibert
Senior Vice President, Industry Affairs
James Skiles
Vice President and General Counsel
Steve Smith
Kellogg Company
Director of Production Planning
Dan Stone
Flowers Foods, Inc.
Vice President of Logistics
Jan Tharp
Christopher West
McCormick & Company, Inc.
Director, U.S. Transportation
Jeffrey Wilke
The Dial Corporation
Director of Distribution Services
Steve Zaffarano
Diamond Foods, Inc.
Vice President, Supply Chain Management and Customer Service
1 Research Bulletin. IC Insights. January 11, 2010. http://www.icinsights.com/news/
2 Occupational Outlook Handbook, 2010-11 Edition. Bureau of Labor Statistics, United States Department of Labor, American Trucking Association. February 4, 2010. http:// www.bls.gov/oco/ooh_index.htm
3 IBM Global Chief Supply Chain Officer Study: The Smarter Supply Chain of the Future. IBM Institute for Business Value. February 2009. http://www-935.ibm.com/services/us/ gbs/bus/html/gbs-csco-study.html
4 Ibid.
© 2010 by the Grocery Manufacturers Association (GMA). All rights reserved. No part of this publication may be reprinted or reproduced in any way without written consent from GMA.
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JLR CONSTRUCTION AND AGGREGATES INC. a corporation engaged in the processing and marketing of quality crushed aggregates and ready – mixed concrete is in need of:
- Graduate of BS in Mechanical Engineering
- Must have expertise in Heavy Equipment Repair
- Knows how to manipulate & operate basic machine tools and trouble shooting
- Computer literate (word, excel)
- Good verbal and written communication
- Knows how to drive (2 and 4 wheels) with license
Applications for this job are now closed.
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text: My scratch… Editing (section) Thomas/Mickey Mouse 0 You do not have permission to edit this page, for the following reasons: The action you have requested is limited to users in one of the groups: Users, FANDOM Staff, FANDOM Helpers, Wiki Managers, Content Team Members. Please log in to edit this wiki.Joining My scratchpad Wiki is free, and it only takes a minute.We hope that you sign in, and become a member of the community!Click here to log in or create an account more + You can view and copy the source of this page: ==Cast== *Thomas as Mickey Mouse *Percy as Goofy *Emily as Minnie Mouse *Mavis as Daisy Duck *James as Donald Duck *Bertie as Pluto *Gordon as Casey Jr. *Skarloey as Huey *Sir Handel as Dey *Peter Sam as Louie *Edward as Scrooge McDuck *Donald as Chip *Douglas as Dale *Henry as Launch McQuack *Diesel as Pete *Diesel 10 as The Robot Butler Return to Thomas/Mickey Mouse. Retrieved from "https://my-scratchpad-wikia.fandom.com/wiki/Thomas/Mickey_Mouse" Edit summary Preview Mobile Desktop Show changes


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text: Today we held a webinar for our Jive Cloud customers who currently use Bunchball for gamification purposes and discussed why Jive Rewards is a better option for them moving forward. The webinar focused on four key areas: Why should they move to Rewards? A brief background about Rewards, including it's interface, admin console and reporting… Show more


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Amara Goes to Washington
Congratulations to Amara Huddleston on being one of only 42 individuals nationwide selected as a 2019 John A. Knauss Marine Policy Fellow, through NOAA Sea Grant (see announcement here). This fellowship will allow Amara to work directly in the federal government in Washington, D.C. during 2019. Past AEL members to receive this honor include: Felix Martinez (2003; Program Manager at NOAA Great Lakes Environmental Research Laboratory), LeAnn Southward Hogan (2004; Senior Policy Advisor, Office of National Marine Sanctuaries, NOAA), Gene Kim (2005; National Program Leader, Aquaculture, USDA, National Institute of Food and Agriculture).
We wish Amara the best and look forward to seeing where her path takes her!


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The double sided suction cup is made of 100% silicone! A must have, attach almost any dildo to another and create your own double-ended dildo. Alternatively, turn your dildos into suction cup dildos in a snap. This product is compatible with most dildos; the suction cup diameter is 2.5 inches and can support dildos up to 3 pounds.
Introducing our new double sided suction cup.
Made of 100% silicone this matte black double sided suction cup is a must. Attach just about any dildo to a) another dildo or b) a flat surface. Turn your dildos into suction cup dildos and double ended dildos in a snap. This product is compatible with all of our products and most high end dildo. The suction cup diameter is 2.5 inches and can support dildos up to 3 pounds.
Made by New York Toy Collective.
|2 oz
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A gift card redeemable at our Eugene location, mailed to your front door.
30 seductive activities
Stabilize your favorite toy with the Suction Cup from Tantus! This suction cup is compatible for all Tantus toys that utilize a bullet.
A must-have for anyone practicing rope bondage, these medical grade paramedic-style safety shears are perfect for quick removal of rope in an emergency without damaging a person's skin. Additionally, the manageable finger loops make for an easy and comfortable grip. The protective tab at the tip leads to quick and safe rope snipping. Because of […]
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Senator Carlucci Joined East Ramapo School Officials to Support Legislation Ensuring NYS Schools Do Not Lose Funding Due to the Coronavirus
(Spring Valley, NY) – Senator David Carlucci (D-Rockland/Westchester) joined East Ramapo Central School District Superintendent Dr. Deborah Wortham, nursing and facilities staff, and Rockland County Legislator Tony Earl at Spring Valley High School today to discuss potential funding impacts due to school closures.
The East Ramapo Central School district had three students test positive for the coronavirus at three different schools in the district, including: Pomona Middle School, Ramapo High School, and Hempstead Elementary School. The 14 schools in the district have been closed since Saturday, and 2,500 people have self quarantined.
Ahead of the State's emergency declaration, Carlucci introduced emergency legislation (S.7996A) last week to proactively ensure New York's schools do not lose funding if they cannot meet 180 days of instruction due to a confirmed case or a closing out of an abundance of caution.
If schools do not reopen soon in the East Ramapo School District, they could begin losing $210,000 a day in education funding.
Senator David Carlucci said, "Our school districts have been put in a very difficult situation where they are forced to decide between the health and welfare of the students, teachers and staff and the financial well-being of the district. Its an unfair situation, and we need clarity from the State Education Department and Albany. We have legislation pending right now that would give crystal clear guidance that if a district needs to close, they could do that without jeopardizing their State aid."
East Ramapo Central School District Superintendent, Dr. Deborah Wortham, said, "Losing the funding would have a major impact, which is why we have been doing everything we can to ensure that does not happen. When I heard Senator Carlucci's voice on the phone, it sort of brought tears, because it takes an entire village to raise a child, and this is what it looks like. We thank him for championing this legislation to ensure we are whole."
Schools usually prepare for a number of potential snow days; however, the East Ramapo Central School District has already met the limit and was using Spring Break days from April.
However, on Friday, the Governor said that the State will waive the 180 day requirement for school districts under his executive order, only if all snow and vacations days have already been used.
"We have four days for Spring Break, and we took 3 days, and legally we can do that. Why should we though have to take Spring Break days from our teachers," asked Superintendent Dr. Wortham.
Carlucci's legislation would protect teachers and faculty from losing their vacation time, and not require a school to exhaust their time off to meet the 180 day requirement.
Carlucci's legislation is carried by Felix Ortiz in the Assembly and has garnered the support of Education Committee Chair, Shelley Mayer.
The bill is currently in the Education Committee. If passed and signed into law, it would take effect immediately.


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Schreckgespenst Infektionen
Diercke Weltatlas - Aktuelle Ausgabe 2015
Der Lebensfreude Kalender 2021
The Doll Factory
Once Upon a Time... in Hollywood
International Exchange in the Early Modern Book World presents new research on the movement and exchange of books between countries, languages and confessions. It explores commercial networks and business strategies, and the translation and circulation of literature, music and drama.
SOFORT LIEFERBAR (am Lager)
International Exchange in the Early Modern Book World presents new research on several aspects of the movement and exchange of books between countries, languages and confessions. It considers elements of the international book trade, the circulation and collection of texts, the practice of translation and the diffusion and exchange of technical and cultural knowledge. Commercial and logistical aspects of the early modern book trade are considered, as are the relationships between local markets and the internationally-minded firms which sought to meet their expectations. The barriers to the movement of books across borders - political, linguistic, confessional, cultural - are explored, as are the means by which these barriers were surmounted.
Notes on ContributorsPrefacePART ONEThe International Book Trade: Business without Borders1. Sales Channels for Bestsellers in Sixteenth-Century EuropeValentina Sebastiani2. International Publishing and Local Needs: the Breviaries and Missals Printed by Plantin for the Spanish CrownBenito Rial Costas3. Centre and Periphery? Relations between Frankfurt and Bologna in the Transnational Book Trade of the 1600sCaroline Duroselle-Melish4. Selling Books in the Italian Renaissance. The Correspondence of Giovanni Bartolomeo Gabiano (1522)Angela Nuovo5. Plantin and the French Book MarketMalcolm WalsbyPART TWOCultural Transmissions and Political Exchange6. Books as a Means of Transcultural Exchange between the Habsburgs and the OttomansZsuzsa Barbarics-Hermanik7. 'This Book Hath Been Often Call'd For': Translations of Italian Works on the Dutch Revolt and the European Book MarketNina Lamal8. The Pike and the Printing Press: Military Handbooks and the Gentrification of the Early-Modern Military RevolutionMark R. GeldofPART THREELibraries, Collections, Ownership9. How to Build a Library across Early-Modern Europe: the Network of Claude ExpillyShanti Graheli10. Books without Borders. The Presence of the European Printing Press in the Italian Religious Libraries at the End of the Sixteenth CenturyGiovanna Granata11. Angelica's Book: the Power of Reading in Late Renaissance FlorenceBrendan DooleyPART FOURMoving Music and Translating Tongues: Literature and Music between Countries12. Confessional Networks, Cultural Exchange and the Printed Music of Jerome Commelin (ca.1550-1597)Matthew Laube13. Sellers and Buyers of Italian Music around 1700: the Silvani Firm and G.B. Bassani's Music in Italy and Central EuropeHuub van der Linden14. Translating Renaissance Drama: Networks, Platforms, AppsAnston Bosman15. "Catullum Numquam Antea Lectum [...] Lego": a Short Analysis of Catullus' Fortune in the Sixteenth and Seventeenth CenturiesAlina Laura de Luca16. Intertraffic: Transnational Literatures and Languages in Late Renaissance England and EuropeWarren BoutcherIndex
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KNO-SAMMLUNG: Library of the Written Word - The Handpress World Vol.51
KNOABBVERMERK: 2016. XXII, 383 p. With 41 illustrations. 235.0 mm
KNOMITARBEITER: Ed. by Matthew McLean and Sara Barker
Einband: Gebunden
Auflage: XXII, 383 Pp. w
Sprache: Englisch
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Born To Buy
By Schor, Juliet
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Born to Buy: The Commercialised Child and the New Consumer Culture
by Schor, Juliet
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Description:Simon & Schuster Ltd. Hardcover. Used; Good. **Simply Brit** Shipped with Premium postal service within 24 hours from the UK with impressive delivery time. We have dispatched from our book depository; items of good condition to over ten million satisfied customers worldwide. We are committed to providing you with reliable and efficient service at all times. 02/21/2005
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text: It's been another week since Donald Trump was acquitted in Mitch McConnell's sham trial and another week where he has stepped on the gas in his drive toward authoritarianism. This week, Stu and AJ dive into how he's doing just that, from pardoning not only cronies but those whose crimes resemble his own, declaring himself (erroneously) America's top law enforcement official, appoint blindly loyal stooges to critical posts, and even calling for the removal from office of Barack Obama (who, um, isn't in office). Plus! A look at Nevada's caucuses and what it means going forward, the many ways Bernie dominated, and why — whether you support Sanders or not — all Democrats and Trump resisters should be very happy with how things played out. Take Action: Call your senators at 202.224.3121 and tell them to fund election security and pass measures to stop Russia from meddling in our democracy once and for all. Moment of Uplift: At a Catholic school outside of Seattle, Paul Danforth and Michelle Beatty were forced out of their teaching jobs after getting engaged to their same sex partners. It looked like they may have no recourse against the school... until their students got involved. This is your country for the week of February 23, 2020! Produced by Sam Graber Engineered by Mark Charles, recorded at the Ramshackler Room, Louisville, KY Music by Mike Michel


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Cat Food, Canned, Fit & Free, Go!, Chicken, Turkey, Trout, 5.5oz
|Article number:
|In stock
Our GO! FIT + FREE™ Chicken, Turkey + Trout Stew Recipe is prepared with premium quality chicken, turkey + trout, fruits & veggies and omega oils. Our FIT + FREE™ recipes have the most meat of any GO! recipe.
A protein-rich, lower carb diet helps your cat stay strong, healthy and fit.
This recipe also features:
They select the highest quality, healthiest, least processed, and of course the most flavourful ingredients available. Here is a full list of the ingredients used in this recipe:
Chicken, chicken broth, turkey broth, chicken liver, turkey, trout, dried egg whites, peas, carrots, potato starch, potatoes, sweet potatoes, apples, natural flavour, guar gum, red peppers, bananas, broccoli, sodium phosphate, salt, calcium carbonate, potassium chloride, flaxseed, minerals (iron amino acid chelate, zinc amino acid chelate, copper amino acid chelate, manganese amino acid chelate, sodium selenite, potassium iodide), choline chloride, blueberries, vitamins (thiamine mononitrate, vitamin E supplement, niacin supplement, d-calcium pantothenate, pyridoxine hydrochloride, riboflavin supplement, vitamin A supplement, biotin, vitamin D3 supplement, vitamin B12 supplement, folic acid), pumpkin, alfalfa sprouts, taurine, cranberry meal, dried kelp, yucca schidigera extract, beta carotene.


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Domestic market of gift baskets for Tet Holiday bustling The domestic market of gift baskets for Tet Holiday (the Lunar New Year) is bustling with activities as demand for gifts has increased. Supermarkets and shops are being busy with offering the finest quality merchandise for gift baskets to satisfy all tastes. Co.opmart, Big C, Vinmart, Lotte Mart, Mega Market have been displaying various kinds of gift baskets so that customers can choose it easily. Retailers predict that purchase power will increase by 20 percent compared to the same period last year and gift baskets from VND500,000 ($21.5) to VND1 million are expected very popular. Saigon Co.op, which operates the Co.opmart supermarket chain, announced this year, its supermarket chain including Co.opmart, Co.opXtra, Co.op Food are exhibiting gift baskets containing goods with clear origin and high quality. Moreover, customers can enjoy free delivery if they do online shopping of 38 baskets with fix price. The Saigon Co.op also announced it has had 12 special gift baskets for workers pricing from VND125,000 to VND299,000 each or fruit gift baskets from VND299,000 to VND1,999,000 each. Additionally, the supermarket chain is also providing free present wrapping for customers. Saigon Co.opmart Marketing Director Do Quoc Huy… Read full this story
- Chancellor Rishi Sunak unveils £350BILLION coronavirus bailout: Government to offer businesses loans up to £5m, three-month mortgage holidays, and no rates for pubs and restaurants for a YEAR
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We report the synthesis of crystalline two-dimensional covalent organic frameworks (COFs) by connecting hydroxybenzene-aldehyde and acetonitrile building blocks to form cyano-substituted benzofuran linkages. Unlike the majority of COFs that were synthesized based on condensation reactions, the COFs in this report are crystallized from irreversible cascade reactions involving consecutive cyanide migration, ring-closure, and oxidation reactions. The irreversible property endows the COFs with high chemical stability in both acid and base and allows them to be postsynthetically modified to install predesigned functionality under harsh conditions. We highlight that the functionalized COFs serve as exceptional vehicles for superprotonic conductions.
Adsorption-based xylene isomer separation is more energy efficient than conventional processes. Herein, three isostructural Hofmann-type porous coordination polymers (PCPs), {M(Pz)[Ni(CN)4]n} (M = Fe, FePzNi, Co, CoPzNi, and Ni, NiPzNi; Pz = pyrazine) were synthesized and shown to exhibit coordination-dependent lability for the selectivity toward p-xylene over m- and o-xylene.
Since their prediction in 1998 , guest-induced structural transitions in 3 rd generation porous coordination polymers (PCPs) have changed common understanding on the adsorption properties of porous solids. By 2009, the chemistry of local and global dynamic behavior in crystalline porous solids received tremendous interest, with the studies linked under soft porous crystals (SPCs) . Since then, another decade has passed and novel phenomena in SPCs have emerged that require evaluation, particularly regarding their host-guest chemistry. In this contribution, we discuss the fundamental chemistry of SPCs by characterizing their common structural features and the resulting structural softness and transitions. In particular, we focus on the recently emerging properties based on metastable transitions and those arising from local dynamics. By comparing the resulting adsorption properties to those of commonly applied rigid adsorbents, we highlight the potential of SPCs to revolutionize adsorption-based technologies, considering our current understanding of the thermodynamic and kinetic aspects. We provide brief outlines for the experimental and computational characterization of such phenomena and offer an outlook toward next generation SPCs likely to be discovered in the next decade.
To achieve unique molecular-recognition patterns, a rational control of the flexibility of porous coordination polymers (PCPs) is highly sought, but it remains elusive. From a thermodynamic perspective, the competitive relationship between the structural deformation energy (Edef ) of soft PCPs and the guest interaction is key for selective a guest-triggered structural-transformation behavior. Therefore, it is vital to investigate and control Edef to regulate this competition for flexibility control. Driven by these theoretical insights, we demonstrate an Edef -modulation strategy via encoding inter-framework hydrogen bonds into a soft PCP with an interpenetrated structure. As a proof of this concept, the enhanced Edef of PCP enables a selective gate-opening behavior toward CHCl3 over CH2 Cl2 by changing the adsorption-energy landscape of the compounds. This study provides a new direction for the design of functional soft porous materials.
Single-ligand-based electronically conductive porous coordination polymers/metal-organic frameworks (EC-PCPs/MOFs) fail to meet the requirements of numerous electronic applications owing to their limited tunability in terms of both conductivity and topology. In this study, a new 2D π-conjugated EC-MOF containing copper units with mixed trigonal ligands was developed: Cu3 (HHTP)(THQ) (HHTP=2,3,6,7,10,11-hexahydrotriphenylene, THQ=tetrahydroxy-1,4-quinone). The modulated conductivity (σ≈2.53×10-5 â S cm-1 with an activation energy of 0.30â eV) and high porosity (ca. 441.2â m2 g-1 ) of the Cu3 (HHTP)(THQ) semiconductive nanowires provided an appropriate resistance baseline and highly accessible areas for the development of an excellent chemiresistive gas sensor.
There are two categories of coordination polymers (CPs): inorganic CPs (i-CPs) and organic ligand bridged CPs (o-CPs). Based on the successful crystal engineering of CPs, we here propose noncrystalline states and functionalities as a new research direction for CPs. Control over the liquid or glassy states in materials is essential to obtain specific properties and functions. Several studies suggest the feasibility of obtaining liquid/glassy states in o-CPs by design principles. The combination of metal ions and organic bridging ligands, together with the liquid/glass phase transformation, offer the possibility to transform o-CPs into ionic liquids and other ionic soft materials. Synchrotron measurements and computational approaches contribute to elucidating the structures and dynamics of the liquid/glassy states of o-CPs. This offers the opportunity to tune the porosity, conductivity, transparency, and other material properties. The unique energy landscape of liquid/glass o-CPs offers opportunities for properties and functions that are complementary to those of the crystalline state.
The enhancement of gas adsorption utilizing weak interactions in porous compounds is highly demanding for the design of energy-efficient storage materials. Here, we present a rational design for such an adsorption process by using synergistic functions between dynamic motion in a local module and weak but specific host-guest interactions, that is, halogen-bond (XB) interactions in metal-organic frameworks (MOFs). We designed a new porous coordination polymer (PCP), that is, Br-PCP, the pore surfaces of which are decorated with -CH2 Br groups and could be useful for interaction with CO2 molecules. In accordance with our anticipation, in-situ studies suggest that the adsorption step at approximately 54â kPa during CO2 adsorption is indeed facilitated by XB interactions with little change in the structural volume. This approach of integrating flexible XB modules in rigid PCPs is applicable for designing advanced gas storage systems.
The effect of organic ligands on the separation performance of Zr based metal-organic framework (Zr-MOF) membranes was investigated. A series of Zr-MOF membranes with different ligand chemistry and functionality were synthesized by an inâ situ solvothermal method and a coordination modulation technique. The thin supported MOF layers (ca. 1â µm) showed the crystallographic orientation and pore structure of original MOF structures. The MOF membranes show excellent selectivity towards hydrogen owing to the molecular sieving effect when the bulkier linkers were used. The molecular simulation confirmed that the constricted pore apertures of the Zr-MOFs which were formed by the additional benzene rings lead to the decrease in the diffusivity of larger penetrants while hydrogen was not remarkably affected. The gas mixture separation factors of the MOF membranes reached to H2 /CO2 =26, H2 /N2 =13, H2 /CH4 =11.
Direct structural information of confined CO2 in a micropore is important for elucidating its specific binding or activation mechanism. However, weak gas-binding ability and/or poor sample crystallinity after guest exchange hindered the development of efficient materials for CO2 incorporation, activation and conversion. Here, we present a dynamic porous coordination polymer (PCP) material with local flexibility, in which the propeller-like ligands rotate to permit CO2 trapping. This process can be characterized by X-ray structural analysis. Owing to its high affinity towards CO2 and the confinement effect, the PCP exhibits high catalytic activity, rapid transformation dynamics, even high size selectivity to different substrates. Together with an excellent stability with turnover numbers (TON) of up to 39,000 per Zn1.5 cluster of catalyst after 10 cycles for CO2 cycloaddition to form value-added cyclic carbonates, these results demonstrate that such distinctive structure is responsible for visual CO2 capture and size-selective conversion.
Control of the reactivity of hydride (H-) in crystal structures has been a challenge because of its strong electron-donating ability and reactivity with protic species. For metal borohydrides, the dehydrogenation activity and air stability are in a trade-off, and control of the reactivity of BH4 - has been demanded. For this purpose, we synthesize a series of BH4 --based coordination polymers/metal-organic frameworks. The reactivity of BH4 - in the structures is regulated by coordination geometry and neighboring ligands, and one of the compounds [Zn(BH4)2(dipyridylpropane)] exhibits both high dehydrogenation reactivity (1.4 wt% at 179 °C) and high air stability (50 RH% at 25 °C, 7 days). Single crystal X-ray diffraction analysis reveals that H δ+···H δ- dihydrogen interactions and close packing of hydrophobic ligands are the key for the reactivity and stability. The dehydrogenation mechanism is investigated by temperature-programmed desorption, in situ synchrotron PXRD and solid-state NMR.
We describe the preparation of the crystalline and glassy state of a coordination polymer displaying proton conduction and guest-accessible porosity. EXAFS and solid-state NMR analyses indicated that pyrophosphate and phosphate ions are the main proton transporters in the glass and that homogeneously distributed 5-chloro-1H-benzimidazole in the glass provides the porosity.
Crystal melting and glass formation of coordination polymers (CPs) and metal-organic frameworks (MOFs) are rare thermal events. To expand the library of melting CP/MOFs, we utilized anti-crystal engineering in ionic liquids to construct CPs. A combination of Cu+ and 4,4'-bipyridin-1-ium derivatives afforded four melting CPs showing stable liquid and glassy states.
Optimal control of gas adsorption properties in metal-organic frameworks (MOFs) or porous coordination polymers (PCPs) remains a great challenge in the field of materials science. An efficient strategy to capture electron-acceptor-type gas molecules such as nitrogen monooxide (NO) is to use host-guest interactions by utilizing electron-donor-type MOFs/PCPs as host frameworks. Herein, we focus on a highly electron-donating chain compound by using the paddlewheel-type [Ru2 II,II ] complex [Ru2 (2,4,5-Me3 PhCO2 )4 ] (2,4,5-Me3 PhCO2 - =2,4,5-trimethylbenzoate) with the phenazine (phz) linker: [Ru2 (2,4,5-Me3 PhCO2 )4 (phz)] (1). Compound 1 exhibited a specific gated adsorption for NO under gas pressures greater than 60â kPa at 121â K, which finally resulted in approximately seven molar equivalents being taken up at 100â kPa followed by four molar equivalents remaining under vacuum at 121â K; its Rh isomorph (2) with weaker donation ability was inactive for NO. When the sample of 1â4 NO was heated to room temperature, the compound underwent a crystal-to-crystal phase transition to give [Ru2 (2,4,5-Me3 PhCO2 )4 (NO)2 ](phz) (1-NO), involving a post-synthetic nitrosylation on the [Ru2 ] unit, accompanied by an eventful site-exchange with phz. This drastic event, which is dependent on the NO pressure, temperature, and time, was coherently monitored by using several different in situ techniques, revealing that the stabilization of NO molecules in nanosized pores dynamically and stepwisely occurred with the support of strong electronic/magnetic host-guest interactions.
Design of the gas-diffusion process in a porous material is challenging because a contracted pore aperture is a prerequisite, whereas the channel traffic of guest molecules is regulated by the flexible and dynamic motions of nanochannels. Here, we present the rational design of a diffusion-regulatory system in a porous coordination polymer (PCP) in which flip-flop molecular motions within the framework structure provide kinetic gate functions that enable efficient gas separation and storage. The PCP shows substantial temperature-responsive adsorption in which the adsorbate molecules are differentiated by each gate-admission temperature, facilitating kinetics-based gas separations of oxygen/argon and ethylene/ethane with high selectivities of ~350 and ~75, respectively. Additionally, we demonstrate the long-lasting physical encapsulation of ethylene at ambient conditions, owing to strongly impeded diffusion in distinctive nanochannels.
The ability of porous coordination polymers to undergo reversible structural transformations in response to the presence of guest molecules has been intensively investigated for applications such as molecular separation, storage, sensing and signalling processes. Here we report on the direct observation of the highly guest-responsive nature of the surface of a single-crystalline porous coordination polymer, which consists of paddlewheel zinc clusters and two types of ligand, by in situ liquid-phase atomic force microscopy. Observations were carried out in solution at constant temperature (28 °C) by high-speed atomic force microscopy with lattice resolution. A sharp and reversible response to the presence or absence of biphenyl guest molecules was observed, under conditions that can scarcely induce the transformation of the bulk crystal. Additionally, by modulating the surface coordination equilibrium, layer-by-layer delamination events were captured in real time at every ~13 s per frame.
Design of molecular structures showing fast ion conductive/transport pathways in the solid state has been a significant challenge. The amorphous or glassy phase in organic polymers works well for fast ion conductivity because of their dynamic and random structure. However, the main issue with these polymers has been the difficulty in elucidating the mechanisms of ion conduction and thus low designability. Furthermore, the amorphous or glassy state of ion conductive polymers often confronts the problems of structural/mechanical stabilities. Covalent organic frameworks (COFs) are an emerging class of crystalline organic polymers with periodic structure and tunable functionality, which exhibit potential as a unique ion conductor/transporter. Here, we describe the use of a COF as a medium for all-solid-state Li+ conductivity. A bottom-up self-assembly approach was applied to covalently reticulate the flexible, bulky, and glassy poly(ethylene oxide) (PEO) moieties that can solvate Li+ for fast transport by their segmental motion in the rigid two-dimensional COF architectures. Temperature-dependent powder X-ray diffraction and thermogravimetric analysis showed that the periodic structures are intact even above 300 °C, and differential scanning calorimetry and solid-state NMR revealed that the accumulated PEO chains are highly dynamic and exhibit a glassy state. Li+ conductivity was found to depend on the dynamics and length of PEO chains in the crystalline states, and solid-state Li+ conductivity of 1.33 × 10-3 S cm-1 was achieved at 200 °C after LiTFSI doping. The high conductivity at the specified temperature remains intact for extended periods of time as a result of the structure's robustness. Furthermore, we demonstrated the first application of a COF electrolyte in an all-solid-state Li battery at 100 °C.
Gas-sensing materials are becoming increasingly important in our society, requiring high sensitivity to differentiate similar gases like N2 and O2. For the design of such materials, the driving force of electronic host-guest interaction or host-framework changes during the sorption process has commonly been considered necessary; however, this work demonstrates the use of the magnetic characteristics intrinsic to the guest molecules for distinguishing between diamagnetic N2 and CO2 gases from paramagnetic O2 gas. While the uptake of N2 and CO2 leads to an increase in TC through ferrimagnetic behavior, the uptake of O2 results in an O2 pressure-dependent continuous phase change from a ferrimagnet to an antiferromagnet, eventually leading to a novel ferrimagnet with aligned O2 spins following application of a magnetic field. This chameleonic material, the first with switchable magnetism that can discriminate between similarly sized N2 and O2 gases, provides wide scope for new gas-responsive porous magnets.
Gate-opening gas sorption is known for metal-organic frameworks, and is associated with structural flexibility and advantageous properties for sensing and gas uptake. Here, we show that gate-opening is also possible for metal-organic polyhedra (MOPs), and depends on the molecular organisation in the lattice. Thanks to the solubility of MOPs, several interchangeable solvatomorphs of a lantern-type MOP were synthesised via treatment with different solvents. One phase obtained through use of methanol induced a gate-opening effect in the lattice in response to carbon dioxide uptake. The sorption process was thoroughly investigated with in situ powder X-ray diffraction and simultaneous adsorption experiments. Meanwhile, solution processing of this flexible phase using THF led to a permanently porous phase without a gate-opening effect. Furthermore, we find that we can change the metallic composition of the MOP, and yet retain flexibility. By showing that gate-opening can be switched on and off depending on the solvent of crystallisation, these findings have implications for the solution-based processing of MOPs.
We demonstrate a new de novo synthetic methodology to achieve high-temperature-stable compelled composite superhydrophobic porous coordination polymers (PCPs). These new PCPs were achieved based on coordination capabilities of first-row transition metal ions such as Co2+, Ni2+, and Zn2+. The obtained composite PCPs containing a [Zn2M2O]6+ (M = Co or Ni) bimetallic cluster core with open metal sites (OMSs) exhibited distinct isosteric heats of adsorption and surface areas due to the difference in their open metal Lewis acidic sites of solvent-free state. Additionally, these composite PCPs exhibit remarkable superhydrophobic properties with contact angles of 159.3° and 160.8° respectively for Zn-Co and Zn-Ni analogues. This superhydrophobic surface survives even at high temperature for longer time periods. As projected, these new composite PCPs exhibit better surface area and heats of adsorption compared to the PESD-1 (Zn) analogue due to a larger number of OMSs. Moreover, they display selective adsorption toward aromatic solvents such as benzene and toluene over aliphatic solvents such as cyclohexane due to corrugated and terminated aromatic hydrocarbon moieties toward the interactive surface. They also exhibit oil spill cleanup from the water surface in the powder form as well as pellet form up to 385 wt %. This study certainly offers a roadmap for designing and engineering new composite superhydrophobic porous materials for better water and thermal stability along with OMSs. This type of PCP exhibits a wide range of applications especially in catalysis, separation technology, and securing environmental problems such as oil spill cleanup in seawater.
Metal-organic frameworks (MOFs) and porous coordination polymers (PCPs) have been well-recognized as emerging porous materials that afford highly tailorable and well-defined nanoporous structures with three-dimensional lattices. Because of their microporous nature, MOFs can accommodate small molecules in their lattice structure, thus discriminating them on the basis of their size and physical properties and enabling their separation even in the gas phase. Such characteristics of MOFs have attracted significant attention in recent years for diverse applications and have ignited a worldwide race toward their development in both academic and industrial fields. Most recently, new challenges in porous materials science demand processable liquid, melt, and amorphous forms of MOFs. This trend will provide a new fundamental class of microporous materials for further widespread applications in many fields. In particular, the application of flexible membranes for gas separation is expected as an efficient solution to tackle current energy-intensive issues. To date, amorphous MOFs have been prepared in a top-down approach by the introduction of disorder into the parent frameworks. However, this new paradigm is still in its infancy with respect to the rational design principles that need to be developed for any approach that may include bottom-up synthesis of porous soft materials. Herein we describe recent progress in bottom-up "modular" approaches for the synthesis of porous, processable MOF-based materials, wherein metal-organic cages (MOCs), alternatively called metal-organic polyhedra (MOPs), are used as "modular cavities" to build porous soft materials. The outer periphery of a MOP is decorated with polymeric and dendritic side chains to obtain a polymer-grafted MOP, imparting both solution and thermal processability to the MOP cages, which have an inherent nanocavity along with high tailorability analogous to MOFs. Well-ordered MOP assemblies can be designed to obtain phases ranging from crystals to liquid crystals, allowing the fabrication of flexible free-standing sheets with preservation of the long-range ordering of MOPs. Furthermore, future prospects of the modular design for porous soft materials are provided with the anticipation that the bottom-up design will combine porous materials and soft matter sciences, leading to the discovery and development of many unexplored new materials and devices such as MOF-based self-healing membranes possessing well-defined nanochannels. The macroscopic alignment of channels can be controlled by external factors, including electric and magnetic fields, external forces, and modified surfaces (templating and patterning), which are conventionally used for engineering of soft materials.